ABSTRACT In this research, the single-phase tetragon NdMn2-x Ag x Si2 (0 ≤ x ≤ 0.4) alloys were prepared. It was found that the phase transition temperature was decreased by evaluating Ag substitution, which was attributed to the enhancement of orbital hybridization. The thermomagnetic hysteresis disappears for x ≥ 0.2. For Δμ0H of 0–7 T, the values of the maximum magnetic entropy change (the relative cooling power) are 22.2 J/kgK (420.7 J/kg), 20.1 J/kgK (500.5 J/kg), 19.9 J/kgK (552.8 J/kg) and 12.0 J/kgK (300.0 J/kg) in NdMn2-x Ag x Si2 (x = 0, 0.2, 0.3 and 0.4) alloys. The XPS valence band spectra indicate that the density of electron and the hybridization effect is enhanced by increasing the substitution amount of Ag. This is attributed to the fact that the atomic radius of Ag is larger than that of Mn, resulting in the strengthening of the covalent bond between Ag and Si.