Graphene oxide (GO) membranes have shown excellent selectivities in nanofiltration and pervaporation. However, the water transport mechanisms in the unique membrane laminar structure are still not well understood, especially in pervaporation which involves selective permeation and evaporation. Herein, water transport in GO membranes was tested under two different modes: pressure-driven permeation and pervaporation. The pure water flux was found to be 1–2 orders of magnitude higher in pervaporation due to the large capillary pressure induced by evaporation. The water flux in pervaporation was suggested to be limited by evaporation at room temperature but surface diffusion at high temperature.