A series of five compounds, namely [Ba(trien)2]3[SbSe4]2·trien (1) (trien=diethylenetriamine), [(Se3)Cr(en)2(Se2)Cr(en)2(Se3)]2 (2) (en=ethylenediamine), [(pren)3 Eu(Te3)2 Eu(pren)3] (3) (pren=1,3-diaminopropane), [(en)4 Ba(pren)Ba(en)4](Te3)2 (4) and [enH]4[Sn2 Se6] (5), which illustrate the transition of classical polychalcogenides to metalates, are presented, where mixed amine/(poly-)chalcogenide interaction with metal centers are in the focus of interest. A conventional aminothermal synthesis is discussed in comparison with ionothermal approaches. The compounds are considered useful precursors to study in situ interconversion of selenido- and telluridometalates under ionothermal conditions.