Researchers in cryogenic magnetic refrigeration have never stopped pursuing magnetic refrigerants with lower ordering temperatures and larger magnetocaloric effects. Rare earth borates have been found to be potential cryogenic magnetocaloric materials due to their low phase transition temperatures and considerable magnetic entropy changes. Here, two rare earth borates RE8.66(BO3)2(B2O5)O8 (RE = Er, Tm) were successfully fabricated, and the crystallographic and magnetic parameters as well as cryogenic magnetocaloric effects were systematically evaluated. The compounds are deemed to crystalize in a monoclinic structure belonging to space group C2/m. They are both second-order phase transition materials without any long-range order above 2 K. These monoclinic rare earth borates, especially for Er8.66(BO3)2(B2O5)O8, show more considerable low-field magnetocaloric effects than rare earth orthoborates. For ΔH = 1 and 2 T, the values of −ΔSMmax are 5.1 and 11.2 J/(kg K) for Er8.66(BO3)2(B2O5)O8, 3.0 and 5.3 J/(kg K) for Tm8.66(BO3)2(B2O5)O8, respectively. Therefore, they are regarded as potential candidates for cryogenic magnetic refrigeration.