Inorganic quantum dots (QDs) have been introduced onto the exterior surface of hollow carbon nitride spheres (HCNS) to construct an inorganic-polymeric curved heterostructure for solar energy conversion. This hybrid nanoheterostructure cooperates well with cofactors to achieve efficient hydrogen evolution under visible light illumination. The enhanced photocatalytic performance of the heterostructure can be attributed to the unique three-dimensional (3D) hollow architectural framework of HCNS as a polymeric scaffold to form intimate interfacial contact with the QDs by a self-assembly strategy to facilitate surface kinetics of charge separation and mass transfer. Such inorganic-polymer hybrid nanoarchitectures based on controlled deposition of stiff QDs onto the flexible HCNS surface provide a valuable platform for constructing stable photoredox systems for solar-to-chemical conversion. This result promises the great potentials of biostructurally-mimic hollow soft semiconductors in developing photofunctional architectures, with an ample choice of secondary guest species to selectively engineer the interface physicochemistry of the hollow sphere for solar application. (C) 2015 Elsevier B.V. All rights reserved.