Treatment of InCl₃ with three equivalents of NaSeC₅H₃(Me-3)N afforded [In{SeC₅H₃(Me-3)Nb₃ which was characterized by elemental analysis, UV-vis and NMR (¹H. ¹³C, ⁷⁷Se) spectroscopy. The crystal structure of [In{SeC₅H₃(Me-3)N}₃·2.5H₂0 revealed that the central indium atom acquires a distorted octahedral geometry. Thermal behavior of the complex was studied by thermogravimetric analysis. Thermolysis of [In{SeC₅H₃(Me-3)N}₃ in various coordinating solvents, gave different morphologies of indium selenide depending on the reaction conditions. Thermolysis of a 1:1 mixture of [In{SeC₅H₃(Me-3)N}and [Cu{SeC₅H₃(Me-3)N}]₄ in various coordinating solvents gave nanocrystals of copper indium selenide. Both In₂Se₃ and CuInSe₂ were characterized by XRD, EDX, SEM, TEMand SAED techniques.