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The HR spectrum of a 50\u00a0mM aqueous solution at pH 11.3 exhibited two prominent bands at 1577 and 1537\u00a0cm\u22121, standing in sharp contrast to both the IR and 532\u00a0nm Raman spectra of bulk glycerol. Based on examinations of laser power and concentration dependencies, isotope effects, and theoretical calculations, the two HR bands were assigned to the stretching vibration of the O\u2013C=C\u2013C linkage and the mixed COH bending\/HCH wagging mode of glyceraldehyde enediolate, a photoproduct generated via laser-induced radical reactions. Despite its low concentration (\u226460 nM), this species dominates the HR spectrum, most likely owing to a double (one- and two-photon) resonance enhancement effect. 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