In this study, polycrystalline samples of Pr2Mn2O6 (parent phase) and Pr1.5A0.5Mn2O6 (A = Mg, Ba) were prepared using the high-temperature solid-phase reaction method. The effects of Mg and Ba doping on magnetocaloric properties and critical behavior of the parent phase were systematically investigated. Under a magnetic field of 7 T, the relative cooling power (RCP) values of Pr2Mn2O6, Pr1.5Mg0.5Mn2O6, and Pr1.5Ba0.5Mn2O6 were approximately 483.46 J·kg−1, 428.22 J·kg−1, and 479.88 J·kg−1, respectively. The critical behavior analysis revealed that the parent phase showed short-range exchange interactions, while Pr1.5A0.5Mn2O6 (A = Mg, Ba) exhibited long-range exchange interactions. The temperature dependence of the order parameter n was studied under different magnetic fields, confirming the phase transition types and validating the accuracy of the critical exponents obtained. The research findings suggest that both the parent phase and Ba-doped ceramics at the A-site hold promise as magnetic refrigeration materials.