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Hyperspectral unmixing aims at identifying the hidden spectral signatures (or endmembers) and their corresponding proportions (or abundances) from an observed hyperspectral scene. Many existing hyperspectral unmixing algorithms were developed under a commonly used assumption that pure pixels exist. However, the pure-pixel assumption may be seriously violated for highly mixed data. Based on intuitive grounds, Craig reported an unmixing criterion without requiring the pure-pixel assumption, which estimates the endmembers by vertices of a minimum-volume simplex enclosing all the observed pixels. In this paper, we incorporate convex analysis and Craig's criterion to develop a minimum-volume enclosing simplex (MVES) formulation for hyperspectral unmixing. A cyclic minimization algorithm for approximating the MVES problem is developed using linear programs (LPs), which can be practically implemented by readily available LP solvers. We also provide a non-heuristic guarantee of our MVES problem formulation, where the existence of pure pixels is proved to be a sufficient condition for MVES to perfectly identify the true endmembers. Some Monte Carlo simulations and real data experiments are presented to demonstrate the efficacy of the proposed MVES algorithm over several existing hyperspectral unmixing methods.