The ordered titanium dioxide nanofibers (TiO₂NF) are prepared using electrostatic spinning technique. A novel heterojunction structure (Se/TiO₂NF) based on TiO₂NF with p-type selenium (Se) nanoparticles are obtained aiming to improve the spectral selectivity of TiO₂NF, inhibit the recombination of photoelectron-hole, and enhance the responsivity and response speed. The Se/TiO₂NF type II band aligned heterojunction with expanded response range of 300-700 nm exhibits excellent self-powered photoelectric performance without bias voltage. Especially, the Se/TiO₂NF device at 610 nm light shows the responsivity of 21 mA·W^-1, the response rise time and fall time of 30 ms and 47 ms, respectively, which is faster than the response time of TiO₂NF device (rise time of 45 s and fall time of 70 s). The results show that the preparation of heterojunction can achieve high performance photodetectors.