The energy efficiency in solar steam generation by 2D photothermal materials has approached its limit. In this work, we fabricated 3D cylindrical cup-shaped structures of mixed metal oxide as solar evaporator, and the 3D structure led to a high energy efficiency close to 100% under one-sun illumination due to the capability of the cup wall to recover the diffuse reflectance and thermal radiation heat loss from the 2D cup bottom. Additional heat was gained from the ambient air when the 3D structure was exposed under one-sun illumination, leading to an extremely high steam generation rate of 2.04 kg m−2h−1. The 3D structure has a high thermal stability and shows great promise in practical applications including domestic wastewater volume reduction and seawater desalination. The results of this work inspire further research efforts to use 3D photothermal structures to break through the energy efficiency limit of 2D photothermal materials.