The ultrafast internal conversion (IC) of piperidine has been observed by femtosecond time-resolved photoelectron imaging (TRPEI) coupled with time-resolved mass spectroscopy. The time evolution of the parent ion is well described by a rapid dephasing pathway with 62 fs and a slow channel with 184 fs. The fast dephasing is ascribed to the IC from the S-1 state to S-2 state, and the slower one is attributed to the IC through the S-2/S-0 conical intersections. The study provides a general view of the piperidine photophysics, which are driven by the interplay between these excited surfaces and the ground state. (C) 2015 Elsevier B.V. All rights reserved.