The ultrafast dynamics of the second singlet electronically excited state (S2) in ethylbenzene has been studied by femtosecond time-resolved photoelectron imaging. The time evolution of the photoelectron signal can be well described by a biexponential decay: a rapid relaxation pathway with a time constant of 60 ( ± 9) fs and a longer-lived channel on a timescale of 2.58 ( ± 0.22) ps. The rapid relaxation is ascribed to the ultrafast internal conversion from the S2 state to the vibrationally hot S1 state. This internal conversion process has been observed in real time. The slow photoelectron signal reflects the depopulation of secondarily populated high vibronic S1 state.