The increase in global warming due to NOx, CO2, and CH4 harmfully different ecosystems and significantly prejudice world life. A promising methodology in this sense is the pollutant conversion into valuable chemicals from photocatalytic processes by reusable photocatalyst. In this way, the present work aimed to produce a Nb2O5 photocatalyst nanofibers system to convert CO2 by the electrospinning method. Based on the collected data, the nanofibers calcination at 600°C for 2 h resulted in the best condition to obtain a homogeneous surface with an average diameter of 84 nm. As a result, the Nb2O5 nanofibers converted CO2 mostly into CO and CH4, reaching values around 8.5 μmol g−1 and 0.55 μmol g−1, respectively.