Pyrolytic decompositions of (i)Pr2Te, (t)Bu2Te, (allyl)2Te, (2-methylallyl)2Te, and (3-methyl-3-butenyl)2Te were investigated by using a combination of gas chromatography and gas chromatography/mass spectroscopy. Product distributions suggested that several competing pathways were operating. Evidence for tellurium-carbon bond homolysis was observed through variable-concentration and trapping experiments. A beta-hydrogen elimination pathway was proposed to account for the observation of 2-methyl-2-propanetellurol and di-tert-butyl ditelluride in the pyrolysis of ((t)Bu)2Te. Both (i)PrTeH and diisopropyl ditelluride were observed during pyrolysis of (i)Pr2Te. Substituted hexadienes were the predominant product in the pyrolytic decomposition of allyltellurium compounds. The observation of three isomeric dienes during decomposition of (3-methyl-3-butenyl)2Te was inconsistent with an intramolecular pathway, suggesting a bond homolysis pathway for all three allyltellurium complexes. By comparison, decomposition of diallyl selenide yields propene as the major product. An "ene" pathway was proposed to account for these observations. Gas-phase pyrolytic decomposition of a series of unsymmetrical tellurium, MeTeR for R = allyl, 2-methylallyl, tert-butyl, and benzyl, led to the formation of MeTeTeMe and MeTeMe as the only observed Te-containing products. Radical coupling products, 1.5-hexadiene, 2,5-dimethylhexadiene, and bibenzyl, were the only observed organic products. Decomposition proceeded by bond homolysis; MeTe. and R. were generated. Evidence for a competing beta-hydrogen elimination pathway was observed in the decomposition of MeTu(t)Bu. The product distributions from the thermal decomposition of the unsymmetrical tellurium compounds were inconsistent with symmetrization prior to decomposition.