Toward the development of new functional materials with single-mol. magnet (SMM) behavior, novel lacunary Dawson-type polyoxometalate (POM)-based clusters containing lanthanide ions (Dy3+ and Tb3+) were synthesized and their applicability as SMMs was verified.Four discrete complexes were obtained at a mixing ratio of lanthanide ions to lacunary POM clusters of 2:2 or 1:2, yielding K14[Dy2(P2W17O61)2]·52H2O (1), K17[Dy(P2W17O61)2]·52H2O (2), K14[Tb2(P2W17O61)2]·52H2O (3), and K17[Tb(P2W17O61)2]·53H2O (4), which were characterized by single-crystal X-ray structural anal.Detailed measurements of the a.c. (ac) magnetic properties revealed that 1 and 2 exhibited the SMM behavior (Ueff/kB = 2.19 and 22.23 K, τ0 = 9.02 x 10-7 and 4.56 x 10-5 s, Hdc = 3000 and 1000 Oe, resp.), unlike 3 and 4.The distorted geometry of Dy3+ ions in 2 in relation to that in 1 resulted in slow magnetic relaxation caused by SMMs with larger energy barrier values, according to temperature-dependent ac susceptibility measurements and theor. calculationsTherefore, new hybrid materials as SMMs from trivalent lanthanide ions and lacunary POM clusters can be fabricated.This study opens new avenues for constructing next-generation compounds that exhibit interesting slow magnetic relaxation based on the assembly of lanthanide ions and lacunary POMs.