The conversion of CO2 gas from the global emission to methanol can be a route to look at in addressing greenhouse gas (GHG) issues. Photocatalysis has been attracting attention in the conversion of CO2 to methanol, as it is seen to be one of the most viable, economic, and sustainable strategies. The biggest hindrance to the use of metal oxide photocatalysts was the poisoning by sulfur content in the CO2 gas feedstock. Therefore, in the development of photocatalysts using metal oxide-based additives, the metal needs to be in the form of metal sulfides to avoid catalyst poisoning due to the presence of H2S. The magnesium sulfide-based TiO2 (MgS-TiO2) photocatalyst has not been synthesized and studied for its photocatalytic potential. In this study, a novel MgS-TiO2 photocatalyst was synthesized using a combination of wet impregnation and hydrothermal method and characterized to determine the physical and chemical properties of the photocatalyst. Characterization results have shown the presence of MgS on the native TiO2 photocatalyst. The optimization of MgS-TiO2 formulation was conducted, wherein the MgS and TiO2 ratio of 0.5 wt % has been shown to give the highest methanol yield of 229.1 μmol/g·h. The photocatalytic parameter optimization results showed that temperature and catalyst loading were the most important factors that impacted the photocatalytic process. In contrast, reaction time had the least significant effect on the CO2 photocatalytic reduction to methanol. This concludes that the MgS-TiO2 photocatalyst has potential and can be used for the photocatalytic reduction of CO2 to methanol.