The effect of substitution of Al(3+), Ga(3+) and Sc(3+) ions in the Mn(3+) site of La0.5Sr0.5MnO3 on the thermochemical splitting of CO2 to generate CO has been studied in detail. Both La0.5Sr0.5Mn1-xGaxO3 and La0.5Sr0.5Mn1-xScxO3 give high yields of O2 and generate CO more efficiently than La0.5Sr0.5Mn1-xAlxO3 or the parent La0.5Sr0.5MnO3. Substitution of even 5% Sc(3+) (x = 0.05) results in a remarkable improvement in performance. Thus La0.5Sr0.5Mn0.95Sc0.05O3 produces 417 μmol g(-1) of O2 and 545 μmol g(-1) of CO, respectively, i.e. 2 and 1.7 times more O2 and CO than La0.5Sr0.5MnO3. This manganite also generates H2 satisfactorily by the thermochemical splitting of H2O.