In the present contribution, the photocatalytic activity of neat and silicon-doped titanium(IV) oxide or titania fibers obtained by combined sol-gel and electrospinning techniques was reported for the first time. Both the calcination temperature and the presence of the silicon dopant affected a great deal the physical and chemical properties of the as-synthesized titania fibers. Increasing the calcination temperature resulted in the observed decrease in the fraction of the anatase phase and the observed increase in the size of the crystalline domains, while the presence of the silicon dopant caused the crystallite size to decrease and the fraction of the anatase phase to increase. The photocatalytic activity of both the neat and the silicon-doped titania fibers was investigated by following the photooxidative decomposition of methylene blue against that of the reference anatase titania. Both the neat and the silicon-doped titania fibers exhibited much better activity than the reference titania powder. In addition, the presence of silicon dopant enhanced the photocatalytic activity of the obtained titania fibers considerably.