Tridentate carborane [S, S, O] ligands 2a–2b [(HOC₆H₂R₂-4,6)(CH₂)SC(B₁₀H₁₀)C(Ph)₂PS, R = ^tBu (2a), R = Me (2b)] were synthesized and characterized. Reaction of CrCl₃(THF)₃ with the sodium salts of ligands 2a and 2b afford six-coordinated chromium complexes 3a and 3b. EXAFS spectroscopy performed on complex 3a to describe the coordination chemistry of ligand 2a around chromium center. DFT calculations were also performed on complex 3a to analyze the structure. The preliminary screening results revealed that six-coordinated chromium complexes 3a–3b displayed good catalytic activities towards ethylene polymerization in the presence of modified methylaluminoxane. The effect of polymerization parameters such as cocatalyst, reaction temperature, ethylene pressure, and reaction time on polymerization behavior were investigated in detail. The polymer obtained from this homogeneous catalytic reaction has a fibroid morphology.