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In this paper, we consider the conditions under which a given ensemble of two-qubit states can be optimally distinguished by local operations and classical communication (LOCC). We begin by completing the perfect distinguishability problem of two-qubit ensembles-both for separable operations and LOCC-by providing necessary and sufficient conditions for the perfect discrimination of one pure and one mixed state. Then, for the well-known task of minimum error discrimination, it is shown that almost all two-qubit ensembles consisting of three pure states cannot be optimally discriminated using LOCC. This is surprising considering that any two pure states can be distinguished optimally by LOCC. Special attention is given to ensembles that lack entanglement, and we prove an easy sufficient condition for when a set of three product states cannot be optimally distinguished by LOCC, thus providing new examples of the phenomenon known as non-locality without entanglement. We next consider an example of N parties who each share the same state but who are ignorant of its identity. The state is drawn from the rotationally invariant trine ensemble, and we establish a tight connection between the N-copy ensemble and Shor's lifted single-copy ensemble. For any finite N, we prove that optimal identification of the states cannot be achieved by LOCC; however, as N→∞, LOCC can indeed discriminate the states optimally. This is the first result of its kind. Finally, we turn to the task of unambiguous discrimination and derive new lower bounds on the LOCC inconclusive probability for symmetric states. When applied to the double trine ensemble, this leads to a rather different distinguishability character than when the minimum error probability is considered.