O,O-Alkylene dithiophosphate derivatives of halodimethyltellurium(IV) of the type Me2TeX[S(2)POGO](2), where X = Cl, Br, I, G = -CMe2CMe2-, -CH2CMe2CH2-,and -CH2CEt2CH2-, were synthesized in 80-90% yields by the reaction in dichloromethane of the appropriate dimethyltellurium dihalide with equimolar amounts of the salt of one of the dithiophosphoric acids. Similarly were prepared related N,N-dimethyl and N,N-diethyl dithiocarbamates of the type Me2TeX[S2CNR2], where R = Me and Et. The compounds were characterized by elemental analyses, H-1, C-13, P-31, and Te-125 NMR, infrared and Raman spectroscopy, and crystal structures when possible. The crystal structures of Me2TeCl[S2POCMe2CMe2O] (1), Me2TeI[S2POCMe2CMe2O] (3), Me2TeCl[S2CNEt2] (10), Me2TeBr[S2CNEt2] (13), Me2TeI[S2CNEt2] (14), Me2TeBr[S2COMe] (15), and Me2TeBr2 (15) are reported. The immediate environment about tellurium in all molecules is essentially that of a sawhorse structure in which the lone pair is apparently stereochemically active and occupying an equatorial position in a distorted trigonal bipyramid. When secondary intra- and intermolecular interactions are included, alternative descriptions of these solid-state structures may be more appropriate.