For increasingly finer powders, the material-specific separation at high loadings is a challenging task, for instance in recycling processes. Here, a combination of triboelectric charging and electrostatic separation was investigated for powder mixtures of talcum and calcite. The dependencies of the triboelectric charge on the mass loading, the gas velocity, and the mixture ratio were investigated. While higher charge levels were achieved with increasing gas velocity, the mass loading had an opposite effect on the net charge. Although bipolar charge distributions were observed within pure materials and mixtures, electrical neutralization did not occur in the mixtures. Therefore, already in a non-optimized setup, a decent degree of material enrichment (of up to 53 %) was found on the separating electrodes.