AbstractThe rapid development of Internet of Things and artificial intelligence brings increasing attention on the harvesting of distributed energy by using triboelectric nanogenerator (TENG), especially the direct current TENG (DC-TENG). It is essential to select appropriate triboelectric materials for obtaining a high performance TENG. In this work, we provide a set of rules for selecting the triboelectric materials for DC-TENG based on several basic parameters, including surface charge density, friction coefficient, polarization, utilization rate of charges, and stability. On the basis of the selection rules, polyvinyl chloride, used widely in industry rather than in TENG, is selected as the triboelectric layer. Its effective charge density can reach up to ~8.80 mC m−2 in a microstructure-designed DC-TENG, which is a new record for all kinds of TENGs. This work can offer a basic guideline for the triboelectric materials selection and promote the practical applications of DC-TENG.