A family of unprecedented tellurotungstate-based organotin-rare-earth (RE) heterometallic hybrids [H2N(CH3)(2)](6)H12Na2 {[Sn(CH3)W2O4(IN)][(B-alpha-TeW8O31)RE(H2O) (Ac)](2)}(2)center dot 25H(2)O [RE = Ce-III (1), Pr-III (2), Nd-III (3), Sm-III (4), Eu-III (5), Gd-III (6), Tb-III (7); HIN = isonicotinic acid, HAc = acetic acid] were synthesized and characterized by elemental analyses, IR spectra, UV spectra, thermogravimetric analyses, powder X-ray diffraction, and single-crystal X-ray diffraction. The polyoxoanionic skeletons {[Sn(CH3)W2O4(IN)][(B-alpha-TeW8O31)RE(H2O) (Ac)](2)}(2)(20-) of 1-7 are constructed from two symmetrical units{[Sn(CH3)W2O4(IN)][(B-alpha-TeW8O31)RE(H2O) (Ac)](2)}(10-) linked by two acetate connectors, which not only represent the first inorganic-organic hybrid RE-substituted tellurotungstates involving three different organic ligands, but also stand for the first samples of organotin-RE heterometallic polyoxometalate derivatives. The solid-state luminescent emission properties of 2-5 mainly display the characteristic emission bands of REIII cations, whereas during the emission procedure of 7, [B-alpha-TeW8O31](10-) segments make a nonignorable contribution to the PL behavior of 7 accompanying by the occurrence of the intramolecular energy transfer from O -> W LMCT energy to Tb3+ centers. Furthermore, 4@CTAB composites with peanutlike and honeycombed morphologies were prepared by a surfactant cetyltrimethylammonium bromide (CTAB). The time-resolved emission spectra of the 4@CTAB composite with CTAB/4 = 0.033/0.05 consolidate the energy transfer from CTAB to REIII centers. Variable-temperature magnetic susceptibility measurements for 2, 3, and 4 were performed.