A new class of nanostructures were fabricated by one-step hydrothermal reaction of a mixture solution of TiO₂ anatase powder and a Sn-porphyrin, trans-dihydroxo[5,10,15,20-tetrakis(p-tolyl)porphyrinato]tin(IV) [SnTTP], and they were found to be well-crystalline trititanate (H₂Ti₃O₇)-type multilayered nanofibers (TiNFs) intercalated by SnTTP which have lengths in the range of 0.5−1 μm with an average diameter of approximately 50 nm. Based on the femtosecond-diffuse reflectance transient absorption and photoluminescence spectroscopic measurements, the SnTTP-intercalated TiNFs were observed to exhibit efficient optoelectronic properties such as photoinduced electron transfer from deep surface states of trititanate layer to SnTTP, forming an anion radical SnTTP^.•- rapidly in a few picoseconds. These results infer that electrons and holes are effectively separated in the SnTTP−TiNFs upon illumination, and consequently remarkable UV−visible light-sensitive photocatalytic activities as compared to those of free TiNFs and SnTTP, suggesting that the SnTTP-intercalated TiNFs have potential application in development of efficient artificial photosynthetic systems and photoelectronic materials.