To explore the tribo-electrostatic separation effects of various coal samples, and determine the appropriate composition and relative humidity of feeding size, a series of experiments were conducted. The experimental results showed: compared with bituminous coal and lignite, anthracite had better separation effects, and the mixture of lignite and other coal samples had worse separation effects; when the air relative humidity was less than 80%, the tribo-electrostatic separator worked well with considerable separation effects; the feeding containing 70% particles less than 0.074 mm brought about an excellent separation effects.