Girolami joined the faculty of the University of Illinois at Urbana-Champaign in 1983. He has served as Head of the Chemistry Department twice, first from 2000 until 2005 and again from 2013 to 2016.
He is the author of several textbooks, including X-ray Crystallography and Synthesis and Technique in Inorganic Chemistry. He was the co-editor of volume 36 of Inorganic Syntheses.
Girolami is also co-founder of a university spin-off company, [http://www.tiptek.com/ Tiptek LLC], which manufactures ultrasharp probe tips for use in scanning tunneling microscopy and for fault diagnosis and testing of integrated circuits. The company has patented its field-directed sputter sharpening (FDSS) technology, which was originally developed in the laboratories of Girolami and fellow UIUC Professor Joseph Lyding.