AbstractAgile nanostructure architectures and smart combinations of semiconducting metal oxide materials are key features of high‐performing dye‐sensitized solar cells (DSSCs). Herein, we synthesize mesoporous solid nanospheres of ZnO–TiO2 with type‐II heterojunction and use these as an efficient photoanode material for excellent photoconversion. These polydisperse aggregates doped with 1 %, 5 %, and 10 % of ZnO exhibit improved solar cell performance with respect to pristine TiO2 under AM 1.5 G. The 1 % ZnO doped TiO2 nanosphere possess high specific surface area (84.23 m2 g−1) as a photoanode and shows high photoconversion efficiency of about 8.07 % with ca. 18 % improvement in the photocurrent density (Jsc) compare to TiO2 nanosphere. The improved solar cell performance (Δη=40 %) of ZnO decorated TiO2 nanospheres is ascribed to type‐II heterojunction of ZnO–TiO2, that reduces the electron recombination and synergistically enhances the electron mobility and charge collection capability.