Graphene oxide (GO) is one of the most attractive inorganic nanofillers in proton exchange membranes (PEMs) for its large specific surface area and high proton conductivity. The proton conductivity of GO nanosheet is known to be orders of magnitude greater than the bulk GO, thus it is essential to improve the dispersion of GO nanosheets in the PEM matrix to achieve higher conductivity. In this study, we report a facile and effective method to fabricate a GO/sulfonated poly ether ether ketone (SPEEK) composite membrane with well-dispersed GO nanosheets in SPEEK matrix by using electrospinning technique for direct methanol fuel cell application. The composite membrane exhibits improved proton conductivity, dimensional stability and methanol barrier property due to the presence of well-dispersed GOs. It is believed that the GO nanosheets can not only induce continuous channels for proton-conducting via Grotthuss mechanism, but also act as methanol barriers to hinder the methanol molecules from passing through the membrane.