Abstract It is a central fact in quantum mechanics that non-orthogonal states cannot be distinguished perfectly. In general, the optimal measurement for distinguishing such states is a collective measurement. However, to the best our knowledge, collective measurements have not been used to enhance quantum state discrimination to date. One of the main reasons for this is the fact that, in the usual state discrimination setting with equal prior probabilities, at least three copies of a quantum state are required to be measured collectively to outperform separable measurements. This is very challenging experimentally. In this work, by considering unequal prior probabilities, we propose and experimentally demonstrate a protocol for distinguishing two copies of single qubit states using collective measurements which achieves a lower probability of error than can be achieved by any non-entangling measurement. Additionally, we implemented collective measurements on three and four copies of the unknown state and found they performed poorly.