Hollow TiO2 fibers were fabricated by electrospinning an aqueous solution of poly(ethylene oxide) (PEO) and introducing the thread-like droplets directly into a titanium tetraisopropoxide (TTIP)/hexane solution, inducing the rapid hydrolysis and condensation of TTIP at the interface between the PEO solution and TTIP solution. Various hollow structures including submicron hollow fibers, thick fibers with a diameter of tens of micrometers, and spherical micron particles could be systematically synthesized by varying the molecular weight and concentration of PEO solution.