Velocity imaging technique combined with (2+1) resonance-enhanced multiphoton ionization (REMPI) is used to detect primary photodissociation of propionyl chloride. In one-color experiments at 235 nm, the Cl and Cl∗ fragments are produced rapidly, leading to a fraction of translational energy release of 0.37 and 0.35, anisotropy parameters of 1.1 and 0.8, and quantum yield of 0.67 and 0.33, respectively, when initial excitation of the (n, π∗)1CO band is coupled to the (nCl, σC–Cl*)1 repulsive configuration. The resulting propionyl radical with sufficient internal energy may undergo secondary dissociation to yield CO that is characteristic of an isotropic distribution. The REMPI spectra of the CO (0,0) and (1,1) bands are measured, giving rise to a Boltzmann rotational temperature of 1200 and 770 K, respectively, and a Boltzmann vibrational temperature of 2800 K. A minor channel of HCl elimination is not detected, probably because of predissociation in two-photon absorption at 235 nm. In two-color experiments comprising an additional 248 nm photolyzing laser, Cl and Cl∗ are produced with a fraction of translational energy release of 0.43 and 0.40 and anisotropy parameters of 1.0 and 0.6, respectively. The secondary production of CO is not observed although the internal energy partitioned in the propionyl radical is in the proximity of the dissociation barrier. In either experimental scheme, a small component appearing in the center of the Cl and Cl∗ images is proposed to stem from ground state dissociation via internal conversion.