Highly efficient solar light absorption capabilities and quantum yields in photocatalysts are key to their application in photocatalytic fields. Towards this end, TiO2/InVO4 nanofibers (NFs) have been designed and fabricated successfully by a one-pot electrospinning process. The resulting TiO2/InVO4 NFs display excellent visible-light photocatalytic activity, owing to their prominent visible-light absorption and electron-hole separation properties. Time-resolved transient PL spectroscopy demonstrated that the TiO2/InVO4 NFs display longer emission decay times (22.0 ns) compared with TiO2 NFs (15.5 ns), implying that the heterojunction can remarkably suppress the electron-hole recombination and promote the carrier transfer efficiency. With tailored heterostructure features, TiO2/InVO4 NFs exhibit superior visible-light photodegradation activity, and after 80 min of visible-light irradiation, almost 95% of RhB molecules can be decomposed by TiO2/InVO4 NFs, while only 18% of RhB molecules can be decomposed by pure TiO2 NFs.