Electrospun nanofibrous TiO2/g-C3N4 heterojunction photocatalysts with different TiO2 content have been synthesized via a facile electrospinning and subsequent in situ evaporation and calcination process for the first time, which are examined in terms of morphology, component content, optical properties, PL spectra, photocurrent response, EIS measurement, photocatalytic activity and mechanism. SEM images exhibit TiO2/g-C3N4-4 heterojunction photocatalyst possesses the excellent 1D structure. HRTEM and element mapping images confirm the formation of heterojunction structure. DRS tests identify that TiO2/g-C3N4-4 heterojunction exhibits the intensitive absorption in both UV and visible light region. The photoelectrochemical tests prove that the recombination between electrons and holes are effectively inhibited. Based on TG analysis and photodegradation experiments, TiO2/g-C3N4-4 heterojunction photocatalyst with TiO2 content of 29.30 wt% possesses the best photocatalytic degradation efficiency for the RhB among the g-C3N4, TiO2 and their mixture under simulated sunlight irradiation. Moreover, 1D morphology of TiO2/g-C3N4-4 heterojunction photocatalyst is in favor of separating from solution for reuse and transferring the electrons, and maintains a very high photocatalytic degradation efficiency of 96% even after four recycles experiments, which is beneficial for practical application. (C) 2017 Elsevier B.V. All rights reserved.