The reaction of F(²P_3/2,1/2) + HD → HF(v′ = 3) + D was investigated in a rotating-source, crossed-beam machine. The high translational energy resolution afforded by the Doppler-selected time-of-flight technique enabled us to distinguish the differential attributes of the HF(v′ = 3) + D products of the ground state (²P_3/2) reaction from those due to the spin–orbit excited (²P_1/2) one. It was found that the F*(²P_1/2) reactivity is significantly smaller than that for F(²P_3/2), and the two state-to-state angular distributions exhibit remarkable similarities, though some differences were noted. Comparing the results with those concluded previously, we assert that both the adiabatic (F(²P_3/2) + HD) and, in particular, the non-adiabatic (F*(²P_1/2) + HD) reactions are predominantly mediated by a resonance mechanism for the formation of the HF(v′ = 3) + D channel.