Nitrite (NO₂⁻) is one of the common salts in aqueous aerosols, and its photolytic products, nitric oxide (NO) and hydroxyl radical (OH), have potential for use in the oxidation of organic matter, such as dissolved formaldehyde, methanediol (CH₂(OH)₂), which is regarded as the precursor of atmospheric formic acid. In this work, the simulation of UVA irradiation in an aqueous mixture of NaNO₂/CH₂(OH)₂ was carried out via continuous exposure with a 365 nm LED lamp, and the reaction evolutions were probed by in situ and real-time infrared and Raman spectroscopy, which provided multiplexity in the identification of the relevant species and the corresponding reaction evolution. Although performing infrared absorption measurements in aqueous solution seemed impracticable due to the strong interference of water, the multiplexity of the vibrational bands of parents and products in the non-interfered infrared regimes and the conjunction with Raman spectroscopy still make it possible to perform in situ and real-time characterization of the photolytic reaction in the aqueous phase, supplementary to chromatographic approaches. During the 365 nm irradiation, NO₂⁻ and CH₂(OH)₂ gradually decreased, concomitant with the formation of nitrous oxide (N₂O) and formate (HCOO⁻) in the early period and carbonate (CO₃²⁻) in the late period, as revealed by the vibrational spectra. The losses or the gains of the aforementioned species increased with increases in the concentration of CH₂(OH)₂ and the irradiation flux of the 365 nm UV light. The ionic product HCOO⁻ was also confirmed by ion chromatography, but oxalate (C₂O₄²⁻) was absent in the vibrational spectra and ion chromatogram. The reaction mechanism is reasonably proposed on the basis of the evolutions of the aforementioned species and the predicted thermodynamic favorableness.