Abstract: The photodissociation dynamics of 2-bromobutane has been investigated at 264.77 and 264.86 nm by ion-velocity map imaging technique coupled with resonance-enhanced multi-photon ionization. The speed and angular distributions have been derived from the velocity map images of Br and Br*. The speed distributions of Br and Br* atoms in the photodis-sociation of 2-bromobutane at ～265 nm can be fitted using only one Gaussian function indicating that bromine fragments were produced via direct dissociation of C-Br bond. Thecontributions of the excited ³Q₀, ³Q₁, and ¹Q₁ states to the products (Br and Br*) were discussed. It is found that the nonadiabatic ¹Q₁←³Q₀ transition plays an important role for Br photofragment in the dissociation of 2-C₄H₉Br at ～265 nm. Relative quantum yield of 0.621 for Br(²P_3/2) at ～265 nm in the photodissociation of 2-bromobutane is derived. By comparing the photodissociation of 2-C₄H₉Br at ～265 nm and that that at ～234 nm, the anisotropy parameter β(Br) and β(Br*), and relative quantum yield ?(Br) decrease with increasing wavelength, the probability of curve crossing between ³Q₀ and ¹Q₁ decreases with increasing laser wavelength.