The growing demand for solid‐state magnetic cooling, leveraging the magnetocaloric effect requires the discovery of high‐performing magnetocaloric materials (MCMs). Herein, a family of Gd‐containing MCMs is provided, specifically the Gd4.5A0.5Si3O13 (A = K, Na, and Li) oxides, which demonstratse exceptional low‐temperature magnetocaloric performance. Through comprehensive experimental investigations and theoretical calculations on their structural, electronic, and magnetic properties, it is unequivocally confirmed that all of them crystallize in a hexagonal apatite‐type structure (space group P63/m), exhibiting an antiferromagnetic semiconductor ground state with magnetic ordering temperatures below 1.8 K (typically ≈0.7 K for Gd4.5K0.5Si3O13). Furthermore, their remarkable maximum magnetic entropy change (−ΔSMmax) values of 31.85 and 58.22 J kgK−1 for Gd4.5K0.5Si3O13; 25.31 and 55.01 J kgK−1 for Gd4.5Na0.5Si3O13; and 25.15 and 55.77 J kgK−1 for Gd4.5Li0.5Si3O13, under the magnetic field changes of 0‐2 and 0‐5 T, respectively, surpass those of prominent low‐temperature MCMs, including the commercialized Gd3Ga5O12 (≈14.6 and 32.8 J kgK−1) paramagnetic salt. These findings in addition to their high environmental stability position these Gd4.5A0.5Si3O13 oxides as exceptionally promising for practical magnetic cooling applications.