Hierarchical　microspheres　constructed　from　a　TiO2　core　and　a　SnO2　shell　have　been　successfully　fabricated　using　a　one-step　solvothermal　method.　The　synthesized　products　were　characterized　by　XRD,　SEM,　TEM　and　FT-IR　measurements.　It　was　found　that　the　concentration　of　precursor　Sn4+　in　the　reaction　system　plays　a　key　role　in　the　formation　of　the　hierarchical　microspheres.　The　core-shell　microspheres　of　TiO2@SnO2　were　formed　by　a　self-assembly　process,　accompanied　by　the　Kirkendall　effect.　These　core-shell　microspheres　of　TiO2@SnO2　have　been　used　for　the　first　time　as　the　electrode　for　C106　dye-sensitized　solar　cells;　they　exhibited　an　efficiency　of　6.24%.　This　might　be　attributed　to　large　surface　area　and　hierarchical　structure　of　the　microspheres,　leading　to　light　scattering,　an　increase　of　dye　adsorption,　a　suppression　of　charge　recombination　and　prolonging　the　electron　lifetime.　©　2014　Elsevier　Ltd.