Photoreaction mechanisms of 6-hydroxyquinoline (6-HQ) and 7-hydroxyquinoline (7-HQ) in low-temperature argon matrixes have been investigated by Fourier transform infrared (IR) spectroscopy and density-functional-theory (DFT) calculations. A comparison of the observed IR spectra of reactants with the corresponding calculated spectral patterns obtained by the DFT method led to the conclusion that the hydrogen atoms in the O-H group of 6-HQ and in that of 7-HQ are selectively located at the outer position against the quinoline ring. When the matrix samples were irradiated upon UV light around 300 nm, IR spectra of unknown chemical species were observed; they were assigned to the photoreaction intermediates, quinolinoxyl radicals and ketene compounds, produced by eliminations of a hydrogen atom and a hydrogen molecule, respectively. In the photoreaction of 7-HQ, a small amount of keto form was also produced by intramolecular hydrogen-atom transfer from oxygen to nitrogen in an argon cage. Kinetic analyses were made by assuming that 5-ketene and 6-ketene were produced from 6-HQ, while 6-ketene and 7-ketene were produced from 7-HQ. The effective rate constants estimated from the absorbance changes of IR bands against irradiation time revealed that the reaction pathway to produce 6-ketene was minor in both HQs, leading to the conclusion that the conformation of reactants, HQs, plays an important role in the photoproduction of ketenes through biradicals in the Wolff rearrangement.