A two dimensional Cu/Ni based coordination polymer [{Cu-11(4,4'-dipy)(2)}{Ni(CN)(4)}](n)center dot 0.7(C2H6O2)center dot 1.6(H2O) (CP-1) (4,4'-dipy = 1,3-di (4-pyridyl)propane) has been demonstrated as a potential co-catalyst on TiO2 support for hydrogen evolution under UV light. CP-1/TiO2 composite exhibits considerable hydrogen production in comparison with the pristine CP-1 and TiO2 (P25), highlighting that the photocatalytic performance is significantly related with the good separation of photo generated e(-)/h(+) pairs. Different wt. % (2.5, 5 and 7.5%) of CP-1 in CP-1/TiO2 composites were tested for photocatalytic hydrogen production in 5 vol % glycerol/water mixture. The 5 wt % CP-1/TiO2 composite displayed the greatest hydrogen production of 9.2 mmolh(-1)g(-1). The concealed mechanism is divulged on the behalf of results obtained by cyclic voltammetry, photoluminescence and diffused reflectance/UV-visible studies which demonstrate that upon irradiation of UV light, electrons transfer from TiO2 conduction band to CP-1. CP-1 not only grabs the conduction band electrons of titania but also performes as a co-catalyst to reduce the protons into hydrogen. These results are anticipated to direct the forthcoming advancement in creating proficient, cheap semiconductor photocatalysts for solar hydrogen production. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.