The sterically encumbered silyl ligands -ESi(SiMe(3))(3) (E = Se, Te) have been used to prepare the first well-characterized examples of group 2 selenolates and tellurolates. Reaction of HSeSi(SiMe(3))(3) with either dibutylmagnesium or the bis(trimethylsilyl)amides of calcium, strontium and barium in the presence of Lewis bases yielded crystalline alkaline earth selenolates. The magnesium selenolate was crystallized as a TRMPSI complex (TRMPSI = tris((dimethylphosphino)methyl)-tert-butylsilane), while the calcium, strontium and barium compounds were isolated as TMEDA adducts (TMEDA = N,N,N’,N,’-tetramethylethylenediamine). Tellurolysis of dibutylmagnesium in hexane gave the base-free, homoleptic tellurolate compound Mg[TeSi(SiMe(3))(3)](2) as colorless plates in high yield. The bis-THF derivative, prepared by recrystallization in the presence of THF, has been characterized by X-ray crystallography. Reactions between the same group 2 silylamides and two equivalents of HTeSi(SiMe(3))(3) in hexane gave high yields of the corresponding tellurolate complexes of calcium, strontium, and barium, that were isolated and crystallized as their THF adducts. The analogous pyridine complexes were readily prepared by the same reactions in the presence of pyridine. Treatment of the bis(pyridine)magnesium tellurolate with 12-crown-4 results in displacement of both the pyridine and the tellurolate ligands to form the ionic complex [Mg(12-C-4)(2)][TeSi(SiMe(3))(3)](2). X-ray data are as follows : [Mg[SeSi(SiMe(3))(3)](2)(TRMPSI)], space group P2(1)/n, a = 13.905(7) Angstrom, b = 15.975(5) Angstrom, c = 22.55(1) Angstrom, beta = 91.77(3)degrees, V = 5674(6) Angstrom(3), Z = 4; [Sr[SeSi(SiMe(3))(3)](2)-(TMEDA)(2)], space group P2(1)/c, a = 9.388(3) Angstrom, b = 12.322(4) Angstrom, c = 23.65(1) Angstrom, beta = 95.91(3)degrees, V = 2724(3) Angstrom(3), Z = 4; [Ba[TeSi(SiMe(3))(3)](2)(pyridine)(5)], space group C2/c, a = 13.630(2) Angstrom, b = 15.933(2) Angstrom, c = 30.363(4) Angstrom, beta = 97.41(1)degrees, V = 6538(2) Angstrom(3), Z = 4.