SnS, SnSe and SnTe are potentially important semiconductor materials. Here, we describe the application of chalcogen containing SnIV guanidinate precursors for the production of tin(II) chalcogenide nanocrystals. Reaction of the stannylene(II) guanidinate complex [{Me2NC(NCy)2}2Sn] (1) with Ph2E2 (E = S, Se, Te), and CBr4 forms the SnIV complexes [{Me2NC(NCy)2}2Sn(Ch‐Ph)2] (2–4) and [{Me2NC(NCy)2}2SnBr2] (5), respectively. Complex 5 has been subsequently used for the synthesis of the corresponding SnIV mono chalcogenide complexes, [{Me2NC(NCy)2}2Sn = E] (6–8) by the reaction of 5 with Li2E systems. Isolated tin complexes have characterized by elemental analysis, NMR spectroscopy, and the molecular structures of complexes 2–5 determined by single‐crystal X‐ray diffraction. TG analysis showed that complexes 2–4 and 6–8 all have residual masses close to those expected for the formation of the corresponding “SnE” systems. Complexes 6–8 were assessed for their utility in the formation of nanocrystalline materials. The materials obtained were characterized by powder X‐ray diffraction (XRD), field emission scanning electron microscopy (FE‐SEM) and energy dispersive X‐ray analysis (EDX). Analysis showed formation of SnSe and SnTe from complexes 7 and 8, respectively.