We present a study of the physical properties of the La0.6Ca0.4MnO3 and La0.6Ca0.3 Ag0.1MnO3 powder samples. Our synthesized samples were prepared by sol–gel methods. They crystallize in the orthorhombic perovskite structure with Pnma space group. The substitution of calcium by silver induces an increase in cell volume. The magnetocaloric effect was estimated from the magnetic isotherms. With 10% of Ag doped in the La0.6Ca0.4MnO3, we can observe a significant maximum variation of the magnetic entropy −ΔSMax and a relative cooling power RCP near room temperature under an applied magnetic field of 5 T. The RCP varied from 221 to 264 J kg−1 under an applied magnetic field of 5 T for La0.6Ca0.4MnO3 and La0.6Ca0.3Ag0.1MnO3, respectively. The comparison of the values, reported in the reference Gd material, underlines that the proposed oxide material has significant advantages for magnetic refrigeration.