We report the first demonstration of rotational-state selectivity in bond fission. C2HD is prepared in the 5ν1 vibrational-state and photodissociated by ∼ 243.1 nm photons that also probe the H/D fragments. The production of both H and D is greatly enhanced upon rovibrational excitation and is rotational-state dependent. The H/D branching ratio for the photodissociation of C2HD (5ν1) is 1.5 ± 0.2 for J′ = 2 and 4.9 ± 0.5 for J′ = 4. Possible mechanisms for the rotational dependence are discussed.