Over the past 15 years, the electrical performance of direct methanol fuel cells (DMFCs) has increased at least tenfold. With this advancement, portable DMFC-powered devices have come to fruition along with dramatic improvement in small power plant and transportation applications. While the DMFC has a theoretical energy density of 6094 W h/kg, only 1000-3200 W h/kg of this energy is realized in practice. Although most portable power applications only necessitate several W h/kg, performance and cost issues associated with polymer electrolyte membranes (PEMs), anode and cathode catalysts, system design, and operational considerations must be overcome for DMFCs to have a role in the methanol economy. This review covers mostly the chemistry aspects of DMFCs.