The two-laser “pump-probe” photolytic fragmentation fluorescence spectrometry of three octenes and two nonenes is described. Probe-laser-induced C2 fluorescence (Deslandres-d'Azambuja system, C1II
g
→ A1II
u
) is detected. The relative C2 fluorescence intensity and spectral patterns exhibited by each alkene are strongly dependent on the probe-laser wavelength. The dependence of the fragment fluorescence intensity on the probe-laser fluence implies that the “probe” laser induces photofragmentation of intermediate species produced by the “photolysis” laser.