Tribocharger design optimisations presented in the literature are based typically on experimental investigations. While this approach is useful and necessary to evaluate the performance of a design, experimental investigations are limited to studying a finite matrix of parameters. Computational approaches, such as the discrete element method (DEM), offer greater flexibility, however they have not been used previously for tribocharger design optimisation. This work presents a novel approach using the DEM to study the effect of different tribocharger designs on the charging process using particle–wall and particle–particle contact areas as proxies for charge transfer. The bulk sample charge output from the model are compared with bulk charges measured experimentally, showing good agreement. Furthermore, a method to predict approximately the charging behaviour of complex mixtures from linear combinations of the simulation outputs of single species, single size particle samples is presented, demonstrating good agreement.