SiO2/TiO2 hybrid nanofibers were prepared by electrospinning and applied for photocatalytic degradation of methylene blue (MB). The phase structure, specific surface area, and surface morphologies of the SiO2/TiO2 hybrid nanofibers were characterized through thermogravimetry (TG), X-ray diffraction (XRD) analysis, Brunauer–Emmett–Teller (BET) analysis, scanning electron microscopy (SEM), etc. XRD measurements indicated that doping of silica into TiO2 nanofibers can delay the phase transition from anatase to rutile and decrease the grain size. SEM and BET characterization proved that silica doping can remarkably enhance the porosity of the SiO2/TiO2 hybrid nanofibers. The MB adsorption capacity and photocatalytic activity of the SiO2/TiO2 hybrid nanofibers were distinguished experimentally. It was found that, although increased silica doping content could enhance the MB adsorption capacity, the intrinsic photocatalytic activity gradually dropped. The SiO2 (10 %)/TiO2 composite nanofibers exhibited the highest MB degradation rate, being superior to SiO2 (20 %)/TiO2 or pure TiO2.