The degradation and mineralization of acephate in aqueous solutions by 60Co‐γ irradiation were investigated. The acephate was dissolved in different pH buffer solutions and purged for 30 min using anticipate gas. It was found that the degradation ratio of acephate increased gradually with the absorbed dose, and the inorganic ions,
SO42−,
PO43−, and
NH4+, were generated in the irradiated solutions. For the solutions without oxygen, the degradation ratio of acephate in N2‐saturated solutions containing t‐BuOH was the highest, and that in N2‐saturated solutions was higher than that in N2O‐saturated solutions. However, the total concentration of inorganic ions in N2O‐saturated solutions was higher than that in the other solutions. Moreover, the concentration of
NH4+ in N2‐saturated solutions containing t‐BuOH was larger than that of
SO42− and
PO43−, whereas in
N2‐ or N2O− saturated solutions, the concentrations of inorganic ions were in the order of
SO42− >
PO43− >
NH4+. In the air‐saturated and O2‐saturated solutions, it was found that the concentration of inorganic ions generated was in the order of
SO42− >
PO43− >
NH4+. The degradation degree of acephate and the concentrations of inorganic ions in O2‐saturated solutions were higher than those in the air‐saturated solutions. The result showed that both of the oxidative and reductive radicals could degrade the acephate, and the oxidative could improve the mineralization of acephate. It was further concluded that it was easier for the reductive radicals to attack the bonds around N than other bonds around S and P, and the SC and PS bond are easily attacked by oxidative radicals. © 2014 American Institute of Chemical Engineers Environ Prog, 34: 324–332, 2015