Abstract A two dimensional Cu/Ni based coordination polymer [{CuII(4,4ʹ-dipy) 2 }{Ni(CN) 4 }] n ·0.7(C 2 H 6 O 2)·1.6(H 2 O) (CP-1) (4,4ʹ-dipy = 1,3-di (4-pyridyl)propane) has been demonstrated as a potential co-catalyst on TiO 2 support for hydrogen evolution under UV light. CP-1 /TiO 2 composite exhibits considerable hydrogen production in comparison with the pristine CP-1 and TiO 2 (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 /TiO 2 composites were tested for photocatalytic hydrogen production in 5 vol % glycerol/water mixture. The 5 wt % CP-1 /TiO 2 composite displayed the greatest hydrogen production of 9.2 mmolh−1g−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 TiO 2 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. Graphical abstract Image 1 Highlights • A composite of bimetal (Cu/Ni) coordination polymer (CP-1) and TiO 2 is synthesized. • CP-1/TiO 2 composite is utilized as photocatalyst for H 2 generation from water. • The 5 wt % CP-1/TiO 2 composite displayed H 2 production of 9.2 mmolh−1g−1. [ABSTRACT FROM AUTHOR]