One-dimensional TiO2/SiO2 core-shell nanofibers were fabricated using a single-nozzle co-electrospinning process with phase-separated, mixed polymer composite solution. The core and shell are composed of Polyvinylpyrrolidone (PVP) and Polyacrylonitrile (PAN) polymers with uniform distribution of TiO2 and SiO2 nanoparticles (NPs), respectively. The NPs were synthesized via sol-gel reaction, simultaneously, in the respective polymer solutions. The morphologies and structures of the fabricated TiO2/SiO2 core-shell nanofibers were investigated by XRD, FTIR, SEM, EDS and TEM images. The influence of different amounts of TiO2 and SiO2 precursors on the photocatalytic and UV-shielding performance of TiO2/SiO2 core-shell nanofibers were studied. Photocatalytic activity of the nanofibers evaluated by observing photodegradation of Methyl Orange (MO) aqueous solution under irradiation of ultraviolet (UV) light. Our results on the TiO2/SiO2 core-shell nanofibers indicate good potential for superior applications in photocatalytic and UV shielding devices.