Solar cells devices based on inorganic/polymer heterojunction can be a possible solution to harvest solar energy and convert to electric energy with high efficiency through a cost-effective fabrication. The solution-process method can be easily used to produce large area devices. Moreover, due to the intrinsic different charge separation, diffusion or recombination in various semiconductors, the interfaces between each component may strongly influence the inorganic/polymer heterojunction performance. Here we prepared a n-type Ag3CuS2 (Eg = 1.25 eV) nanostructured film through a room-temperature element reaction process, which was confirmed as direct bandgap semiconductor through density function theory simulation. This Ag3CuS2 film was spin-coated with an organic semiconducting poly(3-hexythiophene) (P3HT) or polythieno[3,4-b]-thiophene-co-benzodithiophene (PTB7) film, which formed an inorganic/polymer heterojunction. After constructing it to a solar cell device, the power conversion efficiencies of 0.79% and 0.31% were achieved with simulated solar illumination on Ag3CuS2/P3HT and Ag3CuS2/PTB7, respectively. A possible mechanism was discussed and we showed the charge separation at interface of inorganic and polymer semiconductors played an important role. (C) 2015 Elsevier B.V. All rights reserved.