The conversion of carbon dioxide (CO2) into value-added syngas represents an effective approach for addressing both environmental issues and carbon neutrality issue. However, the slow charge dynamics and low CO2 affinity severely limit the photocatalytic CO2 reduction reaction. In this study, bismuth oxide iodide (BiOI)/zinc titanium oxide (Zn2TiO4) composite nanofibers were successfully prepared by immobilizing BiOI nanosheets on Zn2TiO4 electrospun nanofibers through a solvothermal reaction method. The results of photocatalytic research indicate that the BiOI/Zn2TiO4 composite nanofibers exhibit improved photocatalytic activity in CO2 reduction compared to pristine BiOI nanosheets and Zn2TiO4 nanofibers. The highest carbon monoxide (CO) release rate of BiOI/Zn2TiO4 nanofibers could reach 9.10 µmol‧g−1‧h−1, which is 18.6 times and 6.6 times higher than that of pristine BiOI nanosheets and Zn2TiO4 nanofibers, respectively. The enhanced photocatalytic activity can be credited to the formed BiOI/Zn2TiO4 p-n heterojunction, which can boost electron separation, reduce charge recombination at the interface, and promote the reaction process. The presence of oxygen vacancies in BiOI/Zn2TiO4 nanofibers can not only provide active site to facilitate the adsorption and activation of CO2 molecules, but also adjust the energy band structure of the catalyst to accelerate carriers transfer. After four cycles of testing, the CO release rate of BiOI/Zn2TiO4 nanofibers remains nearly constant, demonstrating its excellent stability. This work develops a feasible strategy to improve the efficiency of photoreduction of CO2 through energy band engineering and surface defect technology.