Polypyrrole (PPy) with different morphologies (e.g., particles, nanotubes, and nanowires) were successfully prepared by adding or without adding different kinds of surfactants through a chemical oxidative polymerization method, respectively. The results show that the morphologies of PPy can be effectively controlled and have a significantly effects on their thermoelectric properties. The PPy nanowires exhibit the highest electrical conductivity and Seebeck coefficient among the various PPy morphologies, such as particles, nanotubes, and nanowires, so PPy nanowires were chosen to prepare PPy nanowire/graphene thermoelectric composites via a soft template polymerization method using cetyltrimethyl ammonium bromide as the template. Both electrical conductivity and Seebeck coefficient of the PPy nanowire/graphene composites increased as the content of graphene increases from 0 to 20 wt %, and as the measured temperature increases from 300 K to 380 K, which leds to the same trend for the power factor. A highest power factor of 1.01 μWm−1K−2 at ~380 K was obtained for the PPy nanowire/graphene composites with 20 wt % PPy nanowire, which is about 3.3 times higher than that of the pure PPy nanowire.