To explore the effects of ring substitution on dissociation dynamics, the primary photochemistry of 2-ethylpyrrole was explored using ultrafast ion imaging techniques. Photoexcitation to the S-1 state; a pi sigma* state, in the range from 238 to 265 urn results it cleavage of the N-H bond with an H atom appearance lifetime of ca. 70 fs. The insensitivity of this lifetime to photon energy, combined with a small kinetic isotope effect, suggests that tunneling does not play a major role in N-H bond cleavage. Total kinetic energy release spectra reveal modest vibrational excitation in the radical counter-fragment, increasing with photon energy. At wavelengths less than or equal to 248 nm, an additional low kinetic energy H atom loss mechanism becomes available with an appearance lifetime of similar to 1.5 ps, possibly due to. the. population of higher-lying (1)pi pi* states.