Fluorescence-detected Raman-ultraviolet double resonance spectroscopy enables state-selective investigations of vibrational energy transfer in gas-phase acetylene, C2H2. Pulsed coherent Raman excitation of the (ν2 + ν4 - ν4) rovibrational hot band of C2H2(g) is followed by rovibronic probing of collision-induced population transfer to the ν2 vibrational level. This time-resolved spectroscopic technique provides novel kinetic and mechanistic information on the quasi-elastic intermolecular VV transfer process: C2H2(ν2 + ν4) + C2H2(ν = 0) → C2H2(ν2) + C2H2(ν4). The state-to-state second-order rate constant for this process is measured and its relevance to the dynamics of vibrational energy transfer is discussed. The results demonstrate the advantages of rotationally resolved double-resonance tecniques in elucidating vibrational energy transfer processes.