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In arid and semi-arid areas, organic matter decomposition is stimulated by ultraviolet radiation. In this paper, the association between straw decomposition and UV-A exposure was evaluated. Oven-dried rice straw samples were chronically exposed to UV-A radiation and examined periodically for up to 90 days at room temperature. Scanning electron microscopy (SEM) showed that noticeable disintegration of the fiber structure occurred on the irradiated sample surface in comparison to the control. At the end of the UV-A treatment period, straw mass had decreased by 5%, and dissolved organic carbon (DOC) increased by 18%. The content of cellulose, hemicellulose, and lignin of the irradiated straw decreased by 29.3%, 14.4% and 49.3%, respectively. The marked loss of nitrogen and potassium in the exposed straw were also observed. Thermogravimetric analysis (TGA) showed that treatment with UV-A radiation tended to decrease the mass loss rate and the thermal degradation temperature of the straw biomass from 220 degrees C to 208 degrees C. Infrared spectrometric analysis (ATR-FTIR) showed that functional groups, e.g., C-OH and C-O-C, were disrupted obviously due to UV-A exposure. These results suggest that ultraviolet-A irradiation facilitates straw decomposition by direct photochemical degradation.