Structural and optoelectronic properties of silicon (Si) nanowire-silver indium selenide (AgInSe2) thin film heterojunctions were investigated. The metal-assisted etching method was employed to fabricate vertically aligned Si nanowire arrays. Stoichiometric AgInSe2 films were then deposited onto the nanowires using co-sputtering and sequential selenization techniques. It was demonstrated that the three-dimensional interface between the Si nanowire arrays and the AgInSe2 thin film significantly improved the photosensitivity of the heterojunction diode compared to the planar reference. The improvements in device performance are discussed in terms of interface state density, reflective losses and surface recombination of the photogenerated carriers, especially in the high-energy region of the spectrum.