The S-alkyl trithiocarbonate (trixanthate) derivatives Me3Ge[S2CSR], Ph3Ge[S2CSR], and Ph2Ge[S2CSR]2, where R = Et, i-Pr, n-Pr, and n-Bu, have been prepared in 73-85% yields by the reaction of the potassium salt of the appropriate trithiocarbonic (trixanthic) acid with iodotrimethylgermane, bromotriphenylgermane, or dichlorodiphenylgermane. The compounds were characterized by infrared, Raman, and H-1 and C-13 NMR spectroscopy. The crystal structure of Ph2Ge[S2CS(i-Pr)]2 was determined, and it crystallizes in space group P1BAR (No. 2) with the cell parameters a = 10.752(9) angstrom, b = 13.36(1) angstrom, c = 9.64(2) angstrom, alpha = 105.8(1)-degrees, beta = 11 3.2(1)-degrees, gamma = 91.79(9)-degrees, V = 1211(3) angstrom3, and Z = 2; R = 0.0638, and R(w) = 0.0626. The environment about germanium is essentially that of a distorted tetrahedron with monodentate linkages resulting in S-Ge-S and C-Ge-C angles of 87.3(2) and 118.1(3)-degrees, respectively, and S-Ge-C angles ranging from 110.3(3) to 113.4(3)-degrees. The Ge-S bond distances are 2.278(5) and 2.284(5) angstrom, and the Ge-C bond distances are 1.925(7) and 1.941(9) angstrom. The terminal (C = S) sulfur atoms are oriented toward the germanium center at distances of 3.224(5) and 3.304(5) angstrom. All of these trixanthate derivatives are unstable as a result of the ready elimination of carbon disulfide.