Crosslinked poly(vinyl alcohol) (PVA) based composite films were prepared as polyelectrolyte membranes for low temperature direct ethanol fuel cells (DEFC). The membranes were functionalised by means of the addition of graphene oxide (GO) and sulfonated graphene oxide (SGO) and crosslinked with sulfosuccinic acid (SSA). The chemical structure was corroborated and suitable thermal properties were found. Although the addition of GO and SGO slightly decreased the proton conductivity of the membranes, a significant reduction of the ethanol solution swelling and crossover was encountered, more relevant for those functionalised with SGO. In general, the composite membranes were stable under simulated service conditions. The addition of GO and SGO particles permitted to buffer the loss and almost retain similar proton conductivity than prior to immersion. These membranes are alternative polyelectrolytes, which overcome current concerns of actual commercial membranes such as the high cost or the crossover phenomenon.