The topic of this review is to briefly present the chemistry of the topological insulators (TIs) based on thallium chalcogenides. Numerous phase diagrams of ternary Tl–BV–X (BV – Sb, Bi; X – Se, Te) systems include TlBVX2 type compounds which exhibit spin polarized topological surface state is evaluated and compiled. Published data on the phase equilibria in the quaternary Tl–Sb–Bi–X and Tl–BV–X–X¢ systems are also reviewed and it has been revealed that their quasiternary Tl2X–Sb2X3–Bi2X3 and reciprocal 3Tl2X+BX↔3Tl2X¢+BX3 subsystems form a wide range of solid solutions based on compounds TlBVX2 and BX3, both confirmed as potential 3D TIs materials. All phase diagrams of analyzed respective systems offer profound possibilities for growth their large single crystals from melt.