Tetra-n-butyl ammonium chloride (TBAC) is a semi-clathrate former that can be used for clathrate-based gas capture and storage since TBAC semi-clathrate has vacant small cages available for entrapping gas molecules under mild conditions. In this study, the phase equilibria and structural information of TBAC + Xe + water systems were experimentally investigated at two different TBAC concentrations (1.0 and 3.3 mol%). The slopes of the three-phase (clathrate [H] - liquid [L] - vapor [V]) equilibrium lines for the TBAC + Xe + water systems altered at one or two points as the pressure and temperature changed, which indicates that this slope change might be caused by the structural transformation of the clathrates that were formed. The powder X-ray diffraction (PXRD) patterns, in situ Raman spectra, and 129Xe nuclear magnetic resonance (NMR) spectra demonstrated that the clathrate structure of the TBAC + Xe + water systems changed from tetragonal (P42/m) or orthorhombic (Pmma) to cubic (Pm3̄n) as the pressure increased. Surprisingly, in the higher-pressure region, TBAC acted as a thermodynamic inhibitor without being enclathrated in the clathrate lattices. The thermodynamic and structural information of the TBAC + Xe clathrates will be helpful for conceptualizing and designing the clathrate-based noble gas or radioactive gas capture and storage process.