In this paper, we propose an experimental scheme for unambiguous quantum state comparison assisted by linear optical manipulations, twin-photons produced from parametric down-conversion, and postselection from the coincidence measurement. In this scheme the preparation of the general two mixed qubit states with arbitrary prior probabilities and the realization of the optimal POVMs for unambiguous quantum state comparison are presented. This proposal is feasible by current experimental technology, and may be used in single-qubit quantum fingerprinting.