An alternative, very simple and improved route to obtain indium(III) tetrahaloindate salts of tetrabutylammonium (TBA)[InX4] – 1a (X = Cl), 1b (X = Br) and 1c (X = I) – in high yields (74 – 82%) was developed. Indium(III) tetrahaloindates were then used as starting materials for the synthesis of In(salen)X complexes 2a (X = Cl, 88%), 2b (X = Br, 94%) and 2c (X = I, 88%). Compounds 2a-c were characterized by FT-IR, Raman, and 1H and 13C NMR spectroscopies. The In-salen complexes were able to promote the CO2 cycloaddition reaction with styrene oxide in mild and solvent-free conditions; complex 2a presented the best performance in the initial screening, achieving quantitative conversion (>99%). The parameters of the catalytic system were optimized, and a series of epoxides were tested as substrates for the production of cyclic carbonates with conversions varying from 38% to quantitative. The present study provides a simple method to cheaply and easily prepare indium(III) complexes and employ them to produce value-added chemicals from CO2.