3D uniform Bi2S3 chrysanthemum-like microspheres with 1D nanowire-assembly were prepared through a facile one-step hydrothermal route, using poly(vinylpyrrolidone) (PVP) as a soft template, and Bi(NO3)3 and thiourea as Bi and S sources, respectively. PVP molecules played an important role in the formation of uniform 3D Bi2S3 nanostructures. The reasonable formation mechanism of uniform chrysanthemum-shaped Bi2S3 microspheres was also proposed. Photovoltaic properties were studied preliminarily to demonstrate potential application in dye-sensitised solar cells for the replacement of scarce platinum as counter electrode.