The phenomenon of contact electrification (CE) has been known for thousands of years, but the nature of the charge carriers and their transfer mechanisms are still under debate. Here, the CE and triboelectric charging process are studied for a metal–dielectric case at different thermal conditions by using atomic force microscopy and Kelvin probe force microscopy. The charge transfer process at the nanoscale is found to follow the modified thermionic‐emission model. In particular, the focus here is on the effect of a temperature difference between two contacting materials on the CE. It is revealed that hotter solids tend to receive positive triboelectric charges, while cooler solids tend to be negatively charged, which suggests that the temperature‐difference‐induced charge transfer can be attributed to the thermionic‐emission effect, in which the electrons are thermally excited and transfer from a hotter surface to a cooler one. Further, a thermionic‐emission band‐structure model is proposed to describe the electron transfer between two solids at different temperatures. The findings also suggest that CE can occur between two identical materials owing to the existence of a local temperature difference arising from the nanoscale rubbing of surfaces with different curvatures/roughness. The effect of temperature on contact electrification (CE) is investigated at the nanoscale. It is found that hotter materials tend to be positively charged while cooler materials tend to be negatively charged in CE. Based on the results, an electron thermal‐emission model is proposed. The temperature effect provides strong evidence for electron transfer in CE.