Semi-clathrates of tetrabutylammonium bromide (TBAB) are investigated for their potential application in the CO2 capture context based on hydrate technology. The three-phase lines of semi-clathrates of CO2-TBAB-H2O and N2-TBAB-H2O are established simultaneously with their structure using in situ Raman scattering performed at high pressure. The preferred crystal phase obtained at ambient pressure from solutions of 5 and 40 wt % TBAB initial concentrations is shown to change upon enclathration of CO2 or N2, or by applying a higher pressure on the system. Deep in the stability field, metastable hydrate phases are occurring at the onset of the formation and correspond to the ones expected under ambient pressure conditions. Depending on the pressure, they progressively transformed into the most stable ones when approaching equilibrium and dissociation points. Besides, it is shown that a 5 wt % TBAB original solution forms preferentially a mixed structure of both type B and type A at low gas pressure with CO2 as the guest gas. A new structure is spectroscopically characterized at pressures higher than ∼2 MPa CO2. Type A is demonstrated to be stable at 5 wt % initial TBAB concentration with N2 as the guest molecule and pressure between 8 and 12 MPa. These structural data address new insights on the relationship between the hydrophilic-anion and hydrophobic-cation intercalation with a guest gas producing hydrophobic interaction in a distorted water lattice.