We propose a method for producing composite materials (hTNO@C60) comprising crystalline C60 particles and hollow-structured TiNb2O7 (hTNO) nanofibers via facile liquid–liquid interface precipitation followed by low-temperature annealing. This allows the systematic design of crystalline C60 as an active material for Li-ion battery anodes. The hTNO@C60 composite demonstrates outstanding cyclic stability, retaining a capacity of 465 mA h g−1 after 1,000 cycles at 1 A g−1. It maintains a capacity of 98 mA h g−1 even after 16,000 ultralong cycles at 8 A g−1. The enhancement in electrochemical properties is attributed to the successful growth and uniform doping of crystalline C60, resulting in improved electrical conductivity. The excellent electrochemical stability and properties of these composites make them promising anode materials.