A series of structure-controlled composite TiO2 fibers combining micro- and nanostructures (hereafter, micro-/nanocomposite) were fabricated using a combination of electrospinning and calcination methods, and their photocatalytic activities were investigated. Smooth microscale fibers were obtained by electrospinning a precursor solution containing tetrabutyl titanate and TiF4. TiO2 nanocrystals formed on the microfibers with the help of HF which was produced from the decomposition of TiF4 in calcination. The size and quantity of TiO2 nanocrystals can be controlled by tuning the mass ratio of TiFi4 in the sol-gel precursor solutions and the calcination time. The obtained micro-/nanocomposite TiO2 fibers were found to exhibit enhanced photocatalytic properties when compared with the bare microfibers. These micro-/nanocomposite structures exhibit the advantages of both the nanocrystals and microfibers, which will lead to new developments in photocatalysis.