Entanglement is a key ingredient for performing information processing protocols. On the other hand, it is known that there may exist non-locality without entanglement. Distinguishing a set of unknown states by local operation and classical communication (LOCC) can be recast as a manifestation of non-locality. Motivated by this fact, we have explored a novel relation between entanglement and LOCC distinguishability of an ensemble of entangled states. We have shown explicitly that an ensemble of LOCC distinguished states is more efficientfor quantum information processing protocol than those states which cannot be discriminated deterministically by LOCC.