Hydrogen evolution reaction (HER) through low-cost and earth-abundant electrocatalysts at low overpotentials is a crucial project to clean energy. Molybdenum dioxide/reduced graphene oxide/polyimide-carbon nanotube (MoO2/RGO/PI-CNT) film was synthesized by a simple electrodeposition method as an efficient catalyst for HER. MoO2 nanoparticles with a small size of 10-20 nm uniformly disperse on the RGO surface. The large quantity and small size of MoO2 nanoparticles afford large surface area for HER, greatly enhancing the electrocatalytic performance of MoO2/RGO/PI-CNT film. The HER electrocatalytic property of MoO2/RGO/PI-CNT film in acidic solution is evaluated by linear sweep voltammetry (LSV). MoO2/RGO/PI-CNT film exhibit a high electrocatalytic activity for HER at a small onset overpotential (-110 mV vs RHE) with a high current density (10.0 mA cm(-2)) and a good stability. The low Tafel slope (68 mV dec(-1)) reveals the Volmer-Heyrovsky mechanism for HER. The comparison between MoO2/RGO/PI-CNT film and other catalysts indicate that the MoO2/RGO/PI-CNT film had a great performance for HER. This work presents a new thought for the synthesis of MoO2/RGO/PI-CNT film as an efficient HER electrocatalyst. (C) 2015 Elsevier B.V. All rights reserved.