This study employs first-principles methods to investigate the ORR catalytic activity of As-doped and AsN co-doped graphene. As atoms, as catalytic active sites, exhibit excellent catalytic activity. Due to the strong interaction between As and N, the stability of the As-N co-doped substrate is enhanced. In particular, As-N4 co-doped graphene not only demonstrates the best thermodynamic and kinetic stability, but also has an ORR overpotential of only 0.53 V. We also propose a method to predict the Gibbs free energy change of the system by calculating the adsorption energies of the adsorbates. This approach can streamline the process by eliminating the need to calculate the Gibbs free energy of the ORR system, making it highly advantageous for future studies on the ORR catalytic activity of multi-impurity co-doped graphene.