Targeting the selective and direct synthesis of tartaric acid (TA), the photochemical reactions of maleic acid (MA) solutions containing H2O2. in various solvents have been investigated using four wavelengths in the UV region between 193 and 351 nm, with high intensity from an excimer laser. All the laser irradiations in H2O resulted in the direct synthesis of TA with lower selectivity and it was found that, with XeF-laser (351 nm) irradiation in 1,4-dioxane, TA is selectively and directly synthesized from MA containing H2O2 of lower concentration at room temperature. On the other hand, none of the irradiations in methanol, N,N-dimethylformamide, acetonitrile, and tetrahydrofuran gave the selective formation of TA. On the basis of these results, the reaction scheme for the selective formation of TA is discussed.