Photodissociation dynamics of CH 3 CFCl 2 (HCFC-141b) and CDCl 3 at 205–209nm have been studied by the photofragment velocity map imaging technique. The velocity distributions and the anisotropy parameters of hydrogen atom and chlorine atom consist of fast and slow components. From these results, the photoexcitation of CH 3 CFCl 2 at 205–209nm is inferred to proceed via a mixture of the A′←A′ and A″←A′ transitions for direct cleavage of the CCl bond, while via the A′←A′ transition for direct cleavage of the CH bond. The photodissociation of CDCl 3 proceeds mainly via the E←A 1 transition for the formation of Cl. The direct CD bond cleavage process is a minor channel and is attributable to the A 1 ←A 1 transition. The photodissociation dynamics of CF 2 Cl 2 and CFCl 3 has also been investigated.