We report the bulk phase behavior of ionic clathrate hydrates of tetra-n-butylammonium bromide (TBAB) formed with a common guest substance: CO2 or CH4. We formed the bulk samples by a classical mixing reactor for gas hydrates, and measured them by the powder X-ray diffraction (PXRD). PXRD patterns of the TBAB+(CO2 or CH4) hydrates formed with 0.32 of TBAB mass fraction in the aqueous phase were obtained. They are consistent with the orthorhombic hydrate (Shimada et al., Acta Crystallogr. 2005; Muromachi et al., Chem. Commun. 2014), but not identical with the other stable phase, i.e., the tetragonal TBAB hydrate (Rodionova et al., J. Phys. Chem. B 2013). When the aqueous solutions are under the substantial pressure of CO2 or CH4 gas, TBAB is likely to form the orthorhombic Pmma and/or Imma phases. A question for the bulk orthorhombic TBAB hydrate phase about the scarce gas incorporation is newly proposed.