The semi conducting properties of doped polyaniline (emeraldine-salt, PANI) elaborated by chemical route are investigated by the photo-electrochemical technique. The band gap is found to be 1.48 eV and the transition is directly allowed. The electrical conduction obeys to an exponential law with activation energy of 0.13 eV. p-type conductivity is evidenced from the cathodic photocurrent. The energy band diagram clearly shows the spontaneous hydrogen photo evolution. The potential of the conduction band of PANI (-0.93 V-SCE) determined from the capacitance measurements is suitably positioned with respect to H2O/H-2 level (-0.66 V-SCE). Therefore, the photocatalytic properties of this material has been evaluated according to the hydrogen generation. The best performance is achieved at pH similar to 7 with a liberation rate of 0.113 mL h(-1) (mg catalyst)(-1) and a quantum efficiency of 0.18% under visible light (29 mW cm(-2)). An increase of 56% is obtained on the hetero-system PANI/TiO2. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.