Alpha radiolysis of nitric acid aqueous solution by a 238Pu source is investigated experimentally and theoretically. The time dependence of the nitrous acid yield on dose rate, nitric acid concentration, and nitrate ion concentration is studied. A novel kinetic model for the α-radiolysis of nitric acid aqueous solution is established, by considering the direct and indirect effects. The simulation results agree well with the experimental data, indicating the validity of our model to treat the reaction paths for generation and consumption of nitrous acid. It is shown that the redox reactions involving Pu cannot be neglected in the α-radiolysis of the solution. The results provide a better understanding of the α-ray radiolysis of aqueous nitric acid.