Reduction of chalcogen‐rich Pb:Ch (1:2) phases in ethane‐1,2‐diamine (en) by elemental alkali metals results in the formation of solutions of [Pb2Ch3]2– of high purity and abundance. In contrast, application of the same reaction conditions to a binary Bi:Te (1:2) phase yields the mononuclear [BiTe3]3– anion. Instead of the expected [Tl2Te3]4– or [Tl2Te2]2– anions, analogous reactions with a Tl:Te (1:1) phase end up with a C–C‐bond cleavage of the solvent en with formation of a salt of the telluridocyanate (N≡C–Te)– anion. Side reactions of en and elemental cesium are presented and metalate solutions are investigated with NMR spectroscopy.