Tribovoltaic devices are attracting increasing attention as motion-based energy harvesters due to the high local current densities that can be generated. However, while these tribovoltaic devices are being developed, debate remains surrounding their fundamental mechanism. Here, we fabricate thin films from one of the world’s most common oxides, TiO2, and compare the tribovoltaic performance under contact with metals of varying work functions, contact areas, and applied pressure. The resultant current density shows little correlation with the work function of the contact metal and a strong correlation with the contact area. Considering other effects at the metal–semiconductor interface, the thermoelectric coefficients of different metals were calculated, which showed a clear correlation with the tribovoltaic current density. On the microscale, molybdenum showed the highest current density of 192 mA cm–2. This work shows the need to consider a variety of mechanisms to understand the tribovoltaic effect and design future exemplar tribovoltaic devices.