The use of carbon dioxide, originated from industrial processes, for gas hydrates production, is currently gaining the interest of researchers, due to the opportunity to increase the rate of methane recovery and, furthermore, to permanently store this green-house gas in solid form. However, the production of CO₂ hydrates requires relatively high pressures and low temperatures and energy costs are often too elevated to make these applications feasible. The use of chemical promoters often allows to get around this problem and innumerable researches describe equilibrium condition for CO₂ hydrates in presence of the most available and competitive promoter. This work deals with the consistent lack of information about molecular and crystalline properties of these compounds, which play a crucial function to improve the efficiency of the process. In this research, CO₂ hydrates were formed in presence of THF and TBAB in high-pressure optical cell. The Raman spectra and hydrates crystalline characteristics were observed in situ. The phase equilibrium results indicated that THF extended the temperature range for the stable presence of hydrates, and the optimal promoting concentration was 4.22 mol%. The same mass fraction of THF with NaCl solution still performed as a promoting effect with a narrow equilibrium temperature range. The structure of crystals was described with accuracy and the variation in crystals’ morphology associated to the presence of each specific additive, was characterized. The CO₂-THF sII hydrate tended to form prismatic shaped crystals, and during the decomposition, the THF molecule separated from the clathrate cage with showing an internal collapse on the crystal scale. The CO₂-TBAB semi-clathrate hydrate is columnar in shape and had a similar decomposition process. This work might help to comprehend CO₂ hydrate storage technology and could give theoretical basis for subsequent applications in the sector.