Bisphenol A epoxy (BAEP) is a widely-used material in daily life, and increasing BAEP wastes are being generated. Pyrolysis is a potential technology for BAEP recovery, but conventional processes are inefficient and high energy-consuming. Herein, Fe-catalyzed pyrolysis process was proposed, and comprehensive comparisons were performed on characteristics of products obtained from BAEP pyrolysis in the presence and absence of iron. The results demonstrated that the addition of iron reduced the decomposition temperature of BAEP by approximately 10–20 °C and promoted the generation of gaseous products, in addition, the appropriate conditions were determined as the iron content of 4%, pyrolysis temperature of 400 °C, holding time of 90 min, and heating rate of 5 °C/min. Moreover, based on the analyses of Py-GCMS for volatiles and XPS for residues, the catalytic mechanism was revealed as the facilitation effect of iron on the conversion of lattice oxygen to adsorbed oxygen. This work would be conducive to energy saving and light products production during BAEP pyrolysis and offer valuable references for studies on the recovery of some other organic materials/wastes.