Aligned and flexible electrospun carbon nanomaterials are used to synthesize carbon/perovskite nanocomposites. The free-electron diffusion length in the CH3NH3PbI3 phase of the CH3NH3PbI3/carbon nanocomposite is almost twice that of bare CH3NH3PbI3, and nearly 95% of the photogenerated free holes can be injected from the CH3NH3PbI3 phase into the carbon nanomaterial. The exciton binding energy of the composite is estimated to be 23 meV by utilizing temperature-dependent optical absorption spectroscopy. The calculated free carriers increase with increasing total photoexcitation density, and this broadens the potential of this material for a broad range of optoelectronics applications. A metal-electrode-free perovskite solar cell (power conversion efficiency: 13.0%) is fabricated with this perovskite/carbon composite, which shows great potential for the fabrication of efficient, large-scale, lowcost, and metal-electrode-free perovskite solar cells.