Hydrolysis of PhTeI(3) in the presence of sodium phenylseleninate and M^(3+) ions (M = Y, Nd, Ce) gives well-defined, bowl-shaped telluroxane clusters. Each of the two half-spheres of the compositions [(PhTe)(18){ML}O(24)]^(7+/8+) ({ML} = {Y(NO(3))(H(2)O)}^(2+) (1), {Nd(NO(3))(H(2)O)^(2+)} (2), or {Ce(NO(3))(2)}^(+) (3)) are connected by two (compound 3) or four (compounds 1 and 2) PhSeO(2)^(-) bridges. The resulting chalcogenoxane spheres have internal volumes of approximately 1500 ų. …