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[Display omitted] • An effective strategy to prevent Cassie-wetting failure of structured hydrophobic surface was proposed by simply coating a single-layer graphene. • Droplets exhibit a stable Cassie-state wetting on graphene-coated surface due to the wetting transparency and water impermeability of graphene. • The modified surface showed a 40–100% increase in condensation rate in 5 h at a subcooling of 40 °C. Structured hydrophobic surfaces often suffer from Cassie-wetting failure due to trapped water in structure gaps for a long-term operation. Sustainable Cassie-wetting on such surface could be achieved by coating an atom-thick and moisture-impermeable graphene on it. Water contact angles were measured to clarify the effect of graphene on wetting, and water impermeability was verified by moisture deposition and evaporation. Sliding angle measurements and vapor condensation were carried out to demonstrate the stable Cassie-state wetting and application. Interestingly we found the graphene does not significantly disrupt the wetting behavior of the structured hydrophobic surface, showing a wettability transparency. Moreover, the impermeability of graphene keeps moisture away from the structure gaps. Owning to the combination of these two properties, droplets on the graphene-coated structured surface exhibit a stable Cassie-state hydrophobic wetting, even under the situation of moisture deposition and evaporation. Using the modified surface, we also found a 40–100% increase in condensation efficiency for a 5-hour vapor condensation at a subcooling of 40 °C. These results suggest an effective strategy to prevent Cassie-wetting failure of structured hydrophobic surface and are expected to promote its further application in more complex conditions. [ABSTRACT FROM AUTHOR]