Magnetic refrigeration technology has received extensive attention due to its application prospects in various fields. The research of magnetocaloric materials is the basis for the development of magnetic refrigeration technology. In this study, the α-Gd2(MoO4)3 was prepared by the high temperature solid state reaction. By X-ray diffraction characterization, α-Gd2(MoO4)3 crystallizes in monoclinic structure (space group C12/c1). Furthermore, its magnetism and magnetocaloric effect are investigated. The magnetic ordering temperature of α-Gd2(MoO4)3 is less than 1.8 K and there is a second-order phase transition. The maximum magnetic entropy changes are 20.8 and 32.7 J kg−1 K−1 under the field changes of 0–2 T and 0–5 T, respectively. Besides, the refrigeration capacity and relative cooling power are 142.0 and 190 J kg−1 under field change of 0–5 T. These properties indicate that α-Gd2(MoO4)3 is an excellent candidate for low temperature magnetic refrigeration.