We report on the synthesis and structural characterization of two series of lanthanide-containing 22-tungsto-2-germanates. The first series corresponds to a family of polyanions with the formula [Ln(beta(2)-GeW11O39)(2)](13-) (Ln(III) = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Gd (6), Dy (7)), and the second series corresponds to a family with the formula [Ln(beta(2)-GeW11O39)(alpha-GeW11O39)](13-) (Ln(III) = Ho (8), Er (9), Tm (10)). All compounds were characterized in the solid state by single-crystal and powder XRD, IR, TGA, and SQUID magnetometry. The polyanions were synthesized in aqueous medium by direct reaction of the monolacunary [beta(2)-GeW11O39](8-) POM precursor with the corresponding lanthanide salts. The structure of the polyanions consists of an 8-coordinated lanthanide ion in a square-antiprismatic geometry, which is sandwiched either between two [beta(2)-GeW11O39](8-) units for 1-7 or between a [beta(2)-GeW11O39](8-) and a [alpha-GeW11O39](8-) unit for 8-10. Furthermore, the effect of the central paramagnetic lanthanide ion on the magnetic behavior of the polyanions was investigated, with the erbium-derivative [Er(beta(2)-GeW11O39)(alpha-GeW11O39)](13-) (9) showing single-molecule magnet (SMM) behavior.