In this work, we demonstrate an electrospinning technique to fabricate TiO2/upconversion nanoparticles (UCNPs)/CdS nanofibers on large scale. In addition, the as-prepared TiO2 nanofibers are incorporated with a high population of UCNPs and CdS nanospheres; this results in Forster resonance energy-transfer configurations of the UCNPs, TiO2, and CdS nanospheres that are in close proximity. Hence, strong fluorescent emissions for the Tm3+ ions including the (1)G(4)(3)H(6) transition are efficiently transferred to TiO2 and the CdS nanoparticles through an energy-transfer process. The as-prepared TiO2/UCNPs/CdS nanofibers exhibit full-spectrum solar-energy absorption and enable the efficient degradation of organic dyes by fluorescence resonance energy transfer between the UCNPs and TiO2 (or CdS). The UCNPs/TiO2/CdS nanofibers may also have enhanced energy-transfer efficiency for wide applications in solar cells, bioimaging, photodynamics, and chemotherapy.