PennACE resulted from a merger of two associations, PaCCS (Pennsylvania College Career Services Association) and AICE (Pennsylvania Association for Internships and Cooperative Education). Beginning in 1990 PaCCS and PAICE, although separate associations, held a joint annual conference. In June 1999, the PAICE executive board formally moved to investigate a merger. Over the next two years, representatives from both associations discussed with each other the benefits and challenges of combining the two associations, and the two executive boards examined the advantages and disadvantages of the merger in their respective board meetings.

In August 2001, the PaCCS executive board voted to pursue a merger and created a committee to work out the legal and financial issues of merging and to write a preliminary constitution for the new association. PaCCS and PAICE decided to make the merger issue the theme of the 2002 annual conference, Merging Experience, Building Futures. The merger was formally proposed to the conference attendees on May 15, 2002, followed by a breakout session in which each association separately discussed and voted on the issue. When the conference attendees were brought back together, it was announced that each association had accepted the merger proposal. The next day, the attendees nominated executive board candidates, discussed possible names for the new association, and adopted the new constitution effective July 1, 2002. During the summer of 2002, the members selected the name of PennACE from a ballot of several possibilities. The first executive board meeting of PennACE was conducted on July 23, 2002 in State College.

The history of PaCCS goes back to 1984 when the first Pennsylvania career services association was formed as PACS (Pennsylvania Association for Career Services). PACS evolved into PaCCS in 1991. The history of PAICE goes back to 1976 when the association was created as CEAP (Cooperative Education Association of Pennsylvania). In 1996, CEAP became PAICE to better represent the role of internships in the association. Unfortunately, the archives of CEAP do not provide the employers for several of its presidents; and whoever served as president in 1984-1985 is a mystery.

A detailed history of the merger and of the associations preceding PennACE is available through the PennACE archives, which are maintained by the current past-president.
Following is a list of those who have served as president of PennACE, PaCCS, PACS, PAICE, and CEAP:
Presidents of PennACE (Pennsylvania Association of Colleges and Employers)
2020-2021, Lesli Somerset Talley, Chatham University 
2019-2020, Jenelle Henry, Kutztown University of PA 
2018-2019, Julie Novotny, Kent State University
2017-2018, Katy Rush, Pennsylvania State University - Harrisburg
2016-2017, Nicole Feldhues, Duquesne University

2015-2016, Heather Balas, Hiram College
2014-2015, Tina Moyer, Lehigh Carbon Community College
2013-2014, Tina Moyer, Lehigh Carbon Community College
2012-2013, Tammy Manko, Indiana University of PA
2011-2012, Kate Carannante, Cedar Crest College
2010-2011, Amy Saul, Moravian College
2009-2010, Kerri Gardi, Kutztown University of PA
2008-2009, Jennifer Mullen, Villanova University
2007-2008, Heather Champion, Dickinson College
2006-2007, Tom Farmar, Enterprise Rent-A-Car
2005-2006, Meaghan Clister, California University of PA
2004-2005, Larry Sechney, Kutztown University of PA
2003-2004, John Snyder, Slippery Rock University of PA
2002-2003, JoAnne Day*, Bloomsburg University of PA
*Term completed by Darwin Kysor, Juniata College
Presidents of PaCCS (Pennsylvania College Career Services Association)
2001-2002, Mark Anthony, Indiana University of PA
2000-2001, Dwayne Keiffer, Messiah College
1999-2000, Kathy Williams, Gettysburg College
1998-1999, Carla Hart, Slippery Rock University of PA
1997-1998, Sandra Slifko, Wilson College
1996-1997, Dave Evans, Lebanon Valley College
1995-1996, Cindy Wilhelm-Ernharth, Elizabethtown College
1994-1995, Deb (Hoffman) Snyder, Messiah College
1993-1994, Becky Campbell, Seton Hill College
1992-1993, Ron Rovansek, University of Pittsburgh - Johnstown
1991-1992, Bill Boyles, Washington & Jefferson University
Presidents of PACS (Pennsylvania Association for Career Services)
1990-1991, Carol Barnett Bloomsburg University of PA
1989-1990, Judy Gardner Waynesburg College
1988-1989*, G. Allan Sternberg, Westminster College & William "Neal" Gutman, Temple University
1987-1988, Patricia McGlynn, Chesnut Hill College
1986-1987, William "Whitney" Martin, Juniata College
1985-1986, Carol Cantini, Duquesne University
1984-1985, Tom Davies, Bloomsburg University of PA
*Sternberg served the remainder of Gutman's term after Gutman's resignation.
Presidents of PAICE (Pennsylvania Association for Internships and Cooperative Education)
2001-2002, Anita Todd, Penn State University
2000-2001, Susan Knell, Penn State University
1999-2000, Marilyn Natili, California University of PA
1998-1999, Yvonne Redd, Indiana University of PA
1997-1998, Diane Fleishman, Millersville University of PA
1996-1997, Gary Hamme, Drexel University
Presidents of CEAP (Cooperative Education Association of Pennsylvania)
1995-1996, Patricia Bazrod, Widener University
1994-1995, Randy Ness, Messiah College
1993-1994, Joanne Schell, Thiel College
1992-1993, Tom Guza, Pennsylvania Power & Light
1991-1992, Grace Hughes, Drexel University
1990-1991, Donna Dentler, Messiah College
1989-1990, Donna Campbell, Saint Vincent College
1988-1989, James Holcomb, University of Pittsburgh
1987-1988, Larry Vold, Indiana University of PA
1986-1987, Joan Gilchrist, Widener University
1985-1986, Marion Mendelson
1983-1984, Elizabeth Scofiled, Philadelphia College of Textiles and Science
1982-1983, Anne Weisbord
1981-1982, William Bradshaw, Pennsylvania College of Technology
1980-1981, Chic Dowburd
1979-1980, Mike Hubbard, Bethlehem Steel
1978-1979, Art Rogers
1977-1978, Ben Baim 
1976-1977, Chuck Hulet