Ion chromatography was used to investigate the effects of γ-ray irradiation dose, vitamin C (VC) content and niacinamide content on nitrite degradation in aqueous solution and spiced donkey meat, and the volatile components of irradiated spiced donkey meat were analyzed by gas chromatography-ion mobility spectrometry. The results showed that γ-ray irradiation could effectively degrade nitrite in both aqueous solution and spiced donkey meat. A synergistic effect was observed when γ-ray irradiation and VC were used together. Nicotinamide had an inhibitory effect on the irradiation degradation of nitrite in aqueous solution, but had a synergistic effect on the irradiation degradation of nitrite in spiced donkey meat. Nitrite ions in aqueous solution were converted to nitrate ions by the irradiation. After 8 or 10 kGy irradiation, the contents of hexanal and heptanal increased, and donkey meat had an off-flavor. This study provides technical support and a theoretical basis for the degradation of nitrite in spiced donkey meat by γ-ray irradiation.