In this work, we demonstrate that expanded graphite can be sufficiently dispersed in polymer solution to form suspensions. Thin composite films were prepared by casting and drying the suspensions. The thermoelectric properties of expanded graphite (ExG)-polymer composites were easily modified by chemical doping. Electrically and thermally insulating polymers of PC, PS, and PMMA served as matrix materials. ExG composite films in PC, PMMA, and PS were prepared using thionyl chloride as the p-type dopant and PEI as the n-type dopant. By comparing the electrical conductivity and Seebeck coefficient values of the composite films, we observed that use of an electron acceptor material (thionyl chloride) in composites enhanced electrical conductivity and reduced the value of the positive Seebeck coefficient, which are p-type doping effects. In contrast, when the donor material PEI was used, there was an increase in electrical conductivity and changes in the value and sign of the Seebeck coefficient from positive to negative, confirming n-type doping.