In this work, PEO17-OPV3, a light-emitting amphiphilic molecule. was served as a structure-directing agent to fabricate the nano-hollow rods and microspheres through self-assembling with titania precursors. FT-IR and EDX were employed to examine the composition of these hybrid materials. In the beginning, the microspheres of similar to 1 mu m composed of bundles of nanorods were observed by SEM. By grinding the microspheres, isolated hollow rods of similar to 100 nm in diameter were observed and investigated by TEM and AFM. Two sets of crystalline planes, rutile (110) and (101), in the skin of hollow rods were resolved. As we stained the OPV3 packing domains of hollow rods with RuO4, the rutile layer of the skin was ripped off, and the stained inner layer of similar to 20 mn diameter was clearly identified. On the basis of the experimental evidence, we proposed a cylinder with a core-shell skin model to explain the formation of nano-hollow rods.