High energy density demand is pushing the development of high-voltage cathode materials, which necessitates improved electrochemical stability of other battery components such as binders, electrolytes, and current collectors. Current collectors are considered to be an inactive component but still play an essential role. In this study, a metal-free composite film containing directionally aligned carbon fiber (CF), carbon nanotube (CNT), and polymer (P) was developed to replace aluminum foil as a cathode current collector, which relies on forming an Al2O3 layer to ensure electrochemical stability at high voltage. Each component in the new cathode current collector played a functional role. The CNTs provided uniform current densities, and CFs improved the electronic conductivity and mechanical strength of the composite material. The polymer enhanced the adhesion of the cathode coating with the current collector and provided an impervious support to the cathode materials. The CF-CNT-P composite demonstrated excellent electrochemical and thermal stability. Cathodes coated on the CF-CNT-P composite exhibited lower charge transfer resistance, improved rate capability, and improved cyclic stability compared with the cathodes deposited on conventional aluminum foil. Additionally, the composite current collector was lighter (1.81 mg/cm2 and 15 µm thick) than the commonly used aluminum foil (4.35 mg/cm2 and 15 µm thick), which can increase the cell energy density. Additionally, the CF-CNT-P did not need to be separated from the cathode coating during recycling and can be burnt out with binder, simplifying the recycling process.