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A membrane electrolyte that restricts the methanol cross-over while retaining proton conductivity is essential for better electrochemical selectivity in direct methanol fuel cells (DMFCs). Extensive research carried out to explore numerous blends and composites for application as polymer electrolyte membranes (PEMs) revealed promising electrochemical selectivity in DMFCs of carbon nanomaterial-based polymer composites. The present review covers important literature on different carbon nanomaterial-based PEMs reported during the last decade. The review emphasises the proton conductivity and methanol permeability of nanocomposite membranes with carbon nanotubes, graphene oxide and fullerene as additives, assessing critically the impact of each type of filler on those properties.