The photolysis branching ratios of 2-bromopropane have been investigated near 234 and 267 nm using resonance-enhanced multiphoton ionization with time of flight mass spectrometry. Bromine fragments monitored in this study were produced via direct dissociation of 2-bromopropane, represented by CH3CHBrCH3 -> CH3CHCH3 + Br(P-2(3/2))/Br*(P-2(1/2)). The branching ratios at two different excitation wavelengths were measured to be 0.534 and 0.244, respectively. The results indicated that the Br(P-2(3/2)) dominated the dissociation process and the branching ratios exhibited an increasing trend with photon energy increase. Through ab initio calculation, we proposed a possible photodissociation mechanism of 2-bromopropane. (c) 2005 Elsevier B.V. All rights reserved.