Hybrid Li-ion capacitors (LICs) are a new kind of electrochemical energy storage device with high energy and power densities. In this work, phosphorus-doped TiO2/phosphorus-doped carbon nanofibers (PTO/PC NFs) are fabricated through a simple electrospinning method with disodium hydrogen phosphate as a phosphorus source. Differing from the PTO prepared by hydrothermal method, sol-gel method or calcining treatment at phosphorous atmosphere. The P-doping evenly distributed in PTO/PC NFs and PTO nanoparticles are embedded in PC, which improves the conductivity, structure stability and Li+ ions diffusion of TiO2. As a result, the PTO/PC NFs anode shows high capacities of 329 and 150 mA h g(-1) (0.1 and 2 A g(-1)), long cycle life (201 mA h g(-1) after 1000 cycles at 1 A g(-1), 69 mA h g(-1) after 1000 cycles at 5 A g(-1)), and superior pseudocapacitance (87%, 2 mV s(-1)). Furthermore, the LICs assembled with PTO/PC NFs anode and AC cathode show outstanding capacity of 35 F g(-1) at a current density of 0.1 A g(-1), high energy density of 72 Wh kg(-1) at the power density of 250 W kg(-1), and cycle stability (54%, 10 000 cycles, 1 A g(-1)). This suggests that PTO/PC NFs is a potential anode material for high-performance LICs.