The generation of ions in air has several useful applications, such as electrohydrodynamic (EHD) pumping, air purification and isolation breakdown prevention. In this paper, ion generation processes in atmospheric air are simulated using a Direct Simulation Monte Carlo (DSMC) method. Details of the collision model are discussed. A C++ code is developed to implement the Monte Carlo method with cross-section data compiled from the literature. Self-sustaining discharge and ionization can be reproduced in the simulation under sufficient voltage bias, and the associated trends obtained are similar to those predicted by Paschen’s curve for a parallel-plate configuration.