When excited at lambda = 230 nm, the vinyl radical and acetylene may be detected via fluorescence from C-2(d(3)Pi (g) -->a(3)Pi (u)) using laser-induced fragmentation fluorescence (LIFF). Vinyl photodissociation creates C-2(d(3)Pi (g)) more efficiently than acetylene photodissociation by a factor of 1300-200 depending on the internal excitation of the vinyl radical. The key difference in LIFF efficiency between the two molecules depends on the mechanism for loss of the first H atom. This LIFF process may provide a method for probing the elusive vinyl radical in methane flames.