The electronic spectrum of benzo[e]pyrene (BeP) was recorded using resonance-enhanced multi-photon ionization (REMPI) spectroscopy. A number of bands were observed and assigned to the origin band and vibronic bands of the S-1-S-0 transition. Ab initio calculations were performed to assign the vibrational structures in S-1. The origin band of BeP is well separated in energy from the origin band of benzo[a]pyrene (BaP), an isomer of BeP, and so BeP and BaP can be readily distinguished by the REMPI method, despite having the same mass.