Solar water evaporation assisted by photothermal membranes is considered to be one of the sustainable and cost effective strategies for pure water generation and wastewater treatment. In this work, the self-assembled reduced graphene oxide (rGO) film has been prepared and proposed for direct solar thermal desalination. The morphology, structure, absorbance and desalination performance of rGO film are explored. It is found that the rGO film with optimized microstructure delivers the evaporation rate of 0.87 kg m−2 h−1 with solar thermal conversion efficiency of 46% under one sun illumination. Moreover, the evaporation rate of rGO film is remaining kept at 0.86 kg/m2·h−1 after ten times recycling, demonstrating the superior reusability.