Three new polyoxometalate compounds based on the lacunary Keggin anion [α-GeW 11 O 39 ] 8− and the rare earth cations (Ln=Nd III , Eu III , Tb III ), [(CH 3 ) 4 N] 2.5 H 7.5 [Eu(GeW 11 O 39 )(H 2 O) 2 ] 2 ·4.5H 2 O (1), [(CH 3 ) 4 N] 2 H 8 [Tb(GeW 11 O 39 )(H 2 O) 2 ] 2 ·2.5H 2 O (2) and [Nd 0.5 (H 2 O) 2 ]H 0.5 [Nd 2 (GeW 11 O 39 )(DMSO) 2 (H 2 O) 8 ]·5.5H 2 O (3), have been synthesized and characterized by elemental analysis, inductively coupled plasmas (ICP) analysis, IR spectroscopy, single-crystal X-ray diffraction. The solid-state structures of compounds 1 and 2 consist of one-dimensional linear wires built of [α-GeW 11 O 39 ] 8− anions connected by Eu 3+ /Tb 3+ cations, while in compound 3, the introduction of the organic molecules DMSO (DMSO=dimethyl sulphoxide) leads to a double-parallel chainlike structure constructed by two linear wires {[Nd(1)(GeW 11 O 39 )(DMSO)(H 2 O) 2 ] 5− } n linked by Nd 3+ coordination cation. Furthermore, the luminescent property of compound 1 and the thermal stability of compound 3 were also studied.