Photolysis studies on formic acid (HCOOH) and formate ion (HCOO-) in presence of TiO2, a photocatalyst, as suspension in water were carried out separately using 350 nm ultraviolet light. The products, such as H2, CO, CO2 and CH4, generated during the experiments were monitored with varying the ambient, light exposure time, and the concentration of HCOOH/HCOO-. The yields of CO in all these systems increased with light exposure time. In aerated systems, CO yields were higher in contrast to the deoxygenated (Ar-purged) systems under identical conditions. It is proposed apparently that the formation of CO is taking place during the chemical reduction of in-situ generated CO2, a photo-mineralized product of HCOOH/HCOO?, but not through the direct photodecomposition or photodehydration (CO+H2O) of solute molecules. The rates of CO formation during 1.3 M HCOOH photolysis in presence of TiO2 photocatalyst were evaluated to be 0.21 and 0.13 μl/min in aerated and Ar-purged systems, respectively. As compared with HCOOH systems, the CO yields are lower when 0.2 M HCOONa was exposed to light under identical conditions. The CO growth rates were evaluated to be 0.07 and 0.046 μl min-1 for aerated and deoxygenated HCOONa systems, respectively; moreover, the trend is quite similar to that of the HCOOH system. Under these conditions, the emission of H2 was also observed, and its yield was significantly higher in Ar-purged system as compared with the CO yields. However, in aerated system, the yields of these products were just opposite. The formation of low yield of methane was observed during photolysis of HCOOH/HCOO-ions. In CO2 ambient, the yields of CO and H2 varied drastically with time. Photolysis studies on formic acid (HCOOH) and formate ion (HCOO-) in presence of TiO2, a photocatalyst, as suspension in water were carried out separately using 350 nm ultraviolet light. The products, such as H2, CO, CO2 and CH4, generated during the experiments were monitored with varying the ambient, light exposure time, and the concentration of HCOOH / HCOO-. The yields of CO in all these systems increased with light exposure time. In aerated systems, CO yield were higher in contrast to the It is proposed apparently that the formation of CO is taking place during the chemical reduction of in situ generated CO2, a photo-mineralized product of HCOOH / HCOO®, but not through the direct The rates of CO formation during 1.3 M HCOOH photolysis in presence of TiO2 photocatalyst were evaluated to be 0.21 and 0.13 μl / min in aerated and Ar-purged systems, y. As compared with HCOOH systems, the CO yields are lower when 0.2 M HCOONa was exposed to light under identical conditions. The CO growth rates were evaluated as 0.07 and 0.046 μl min-1 for aerated and deoxygenated HCOONa systems, respectively; moreover the trend is quite similar to that of the HCOOH system. Under these conditions, the emission of H2 was also observed, and its yield was significantly higher in Ar-purged system as compared with the CO yields. However, in aerated system, the yields of these products were just opposite. The formation of low yield of methane was observed during photolysis of HCOOH / HCOO-ions. In CO2 ambient, the yield of CO and H2 varied drastically with time.