This work has demonstrated for the first time that MoTe2 nanodendrites can be used as an electrocatalyst toward the hydrogen evolution reaction (HER) in neutral solution. MoTe2 nanodendrites are deposited on Mo doped reduced graphene oxide/polyimide (RGO/PI/Mo) composite substrate by electrochemical method. The nanodendrites structure of MoTe2 and the underlying RGO/PI/Mo substrate facilitate the good HER performance of MoTe2-RGO/PI/Mo film in neutral medium. Especially under illumination condition, it has a greater cathode current at more positive potential. Furthermore, MoTe2 nanodendrites have excellent photo-responsive property, and the potential difference could reach 100 mV. Raman spectroscopy reveals that prepared MoTe2 belongs to 1T'-MoTe2. The comparison between MoTe2-RGO/PI/Mo composite film and other catalysts indicate that the MoTe2-RGO/PI/Mo film have a greater performance for HER in neutral solution, which opens up a promising pathway for the exploration of high-efficiency neutral electrocatalysts for HER. (C) 2017 Elsevier Ltd. All rights reserved.