Upconversion nanoparticles/semiconductor nanocomposites have received intense interest in the past two decades. In this work, we demonstrated a facile electrospinning technique and a hydrothermal-assisted crystallization process to fabricate upconversion nanoparticles (UCNPs)/CdS/TiO2 nanofibers successfully. Polyvinylpyrrolidone (PVP, M-w approximate to 1 300000) has been selected as the polymer matrix and tetrabutyl titanate (TBT, 99.0%) was used as the titanium source. The morphologies and phase of the as-prepared samples have been studied using field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). Experimental results revealed that the polymer matrix (PVP) can be dissolved and removed completely under hydrothermal conditions. In addition, the crystalline phase of TiO2 was also achieved under hydrothermal conditions. The as-prepared composite nanofibers are hundreds of micrometers in length and 650 nm in diameter and show weak upconversion fluorescence under the excitation of near-infrared light (980 nm), indicating the high energy transfer efficiency between upconversion nanoparticles and semiconductors. As expected, the UCNPs/CdS/TiO2 nanofibers may have enhanced photocatalytic performance as they make full use of solar energy using UCNPs as nanotransducers for infrared (IR) light.