The study of contact electrification (CE) between metals and semiconductors has immense research value and relevance in the application of micro- and nanosystems. In this paper, a tellurium (Te) nanofilm of large size and high quality was grown on the surface of a silicon wafer by using the chemical vapor deposition (CVD) technique. The contact electrification between the AFM tip (coated with Pt/Ir) and the Te thin film is systematically analyzed using conductive atomic force microscopy (CAFM) and Kelvin probe force microscopy (KPFM). At zero bias, the frictional charges are determined to be nearly 6.517 μC/m2 with one rub cycle. Furthermore, the number of frictional charges can be increased to −40.729 μC/m2 by applying a relatively small voltage (3 V). Based on the density functional theory (DFT) calculation and energy band theory, the modulation of contact electrification charges can be attributed to the modulation of the Te Fermi level. More importantly, the resistance of Te thin films can be effectively manipulated by regulating the triboelectric charge density. This application offers effective insights into the manipulation and influence of friction charges on nanodevices.