A　complex　nanostructure　of　rutile　TiO2　microspheres　with　ultrasmall　nanorods　on　surfaces　was　prepared　by　a　simple　solvothermal　method.　This　complex　nanostructure　is　different　from　the　hierarchical　structure　of　microspheres　composed　of　nanorods.　The　obtained　complex　nanostructure　possesses　an　epitaxy-like　interface　between　the　nanorod-shell　and　the　sphere-core,　which　often　provides　superior　physical　and　chemical　properties.　The　size　and　morphology　of　the　obtained　rutile　TiO2　complex　nanostructure　were　observed　by　scanning　electron　microscopy　and　transmission　electron　microscopy　(TEM).　Their　intrinsic　crystallography　was　characterized　by　X-ray　diffraction,　high-resolution　TEM,　and　selected　area　electron　diffraction.　Controlled　experiments　were　designed　using　varied　temperatures　and　assistant　reagent　compositions　to　study　their　influences　on　the　crystal　phase　and　morphology　of　TiO2.　The　formation　process　of　this　complex　nanostructure　was　determined　via　time-dependent　experiments.　Its　photoluminescence　spectra　showed　the　strongest　emission　at　about　400nm　with　a　blue-shift.　The　photocatalytic　experiments　demonstrated　the　obtained　complex　nanostructure　had　the　highest　catalytic　efficiency　in　the　five　TiO2　samples　with　different　morphologies.　©　2012　Elsevier　Inc.