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–B^V–X (B^V – Sb, Bi; X – Se, Te) systems include TlB^VX₂ 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 TlB^VX₂ 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.