In this study, polyvinyl alcohol (PVA) - polytetrafluoroethylene (PTFE) - vapor grown carbon fiber (VGCF) sheets are fabricated as a new paper-like thermal interface material (TIM), which is a potential substitute for traditional TIMs. Two types of PVA-PTFE-VGCF sheets were fabricated by using 120 nm and 300 nm PTFE particles. The microstructure shows that the VGCFs were arranged in random directions inside the sheet and interconnected via the aggregate of PVA. 300 nm PTFE particles were well distributed within the sheet, while 120 nm PTFE particles aggregated partially and formed pores nearby. The fabricated sheets have a low thickness of 31.2 um and 28.2 um, and lightweight properties with a density of 0.79 × 106 g·m−3 and 0.91 × 106 g·m−3, respectively. With the addition of 300 nm PTFE particles, the fabricated sheet has higher thermal conductivities of 9.81 W·m−1·k−1 in the in-plane direction and 2.11 W·m−1·k−1 in the through-plane direction. In the high temperature and humidity test, the thermal conductivities of the fabricated sheet were increased due to the rearrangement of PVA and PTFE particles.