To date, the development of solar environmental remediation has shifted more emphasis on the green and simple synthesis of catalyst for CO2 photocatalysis process. Herein, TiO2 photocatalyst was successfully synthesized via hydrothermal method. The effects of the different molar ratio of ascorbic acid C6H8O6, (AA) added during the preparation of TiO2 nanoparticles were comprehensively studied. The characterization of TiO2 nanocrystals was performed via XRD, XPS, DRUV-vis, and FTIR. The results show the AA loading into TiO2 nanoparticles significantly intensified the XRD spectra of anatase structure. In fact, this feature had signified a reactivity of the photocatalyst in the visible region. In an instance, BET surface area was also enhanced with the highest recorded value of 135.14 m2/g for 0.8AA. Meanwhile, the CO2 photoreduction over synthesized TiO2 had produced the highest amount of HCOOH at 39.3 μmol/g cat for 0.8AA within 6 hours of reaction time. Furthermore, the DRUV-vis analysis had illustrated better light absorption ability of 0.8AA. This profound finding is attributed to the correlation between large surface area, pure anatase phase, and high adsorbed water molecules. Therefore, this study had significantly demonstrated the potential of modified TiO2 with AA in CO2 photocatalysis area while simultaneously presents a green and simple method for TiO2 synthesis.