Intramolecular hydrogen-atom migrations in 2-hydroxy-3-nitropyridine have been investigated by low-temperature matrix-isolation infrared (IR) spectroscopy with the aid of density functional theory (DFT) calculation. An IR spectrum measured after deposition was assigned to an enol isomer, the conformation of which is anti in relation to OH versus N in the pyridine ring. When the matrix sample was exposed to UV and visible light (lambda > 350 nm), an IR spectrum consistent with a keto product was observed. During the irradiation, an IR spectrum of a transient species, a photoreaction intermediate between anti-enol and keto, was observed, which was assigned to syn-enol. The bands of syn-enol disappeared completely when the irradiation was stopped, while those of the original isomer, anti-enol, reappeared. No reverse isomerization was observable in the corresponding deuterated species. This led to the conclusion that the isomerization from syn to anti occurs through hydrogen-atom tunneling. On the other hand, an aci-nitro form was produced by UV irradiation (lambda = 365 +/- 10 nm) without visible light. The conformation around the aci-nitro group was determined to be cis-cis by comparison with the spectral patterns obtained by the DFT/B3LYP/6-31++G** calculation. The dynamics of the hydrogen-atom migrations between anti- and syn-enols, syn-enol and keto, and anti-enol and aci-nitro are discussed in terms of the potential surfaces obtained by the DFT calculation.