Semiclathrate hydrates are water-based host-guest materials that consist of water and ionic guest substances such as quaternary ammonium salts. Widely-used tetra-n-butylammonium (TBA) salts are designed for gas selectivity and capacity with respect to the industrial application of these materials. This study reported on the formation of semiclathrate hydrates of TBA carboxylates with guest gas characterized by phase equilibrium measurements and single crystal X-ray diffraction. Specifically, TBA acrylate and TBA butyrate are used for ionic guest substances, and this may induce a tetragonal P4(2)/mmm semiclathrate hydrate structure. In the four systems of (TBA acrylate or TBA butyrate) + (CH4 or CO2) + H2O, the measured three (gas hydrate aqueous) phase equilibrium data exhibited better promotion effects due to the TBA acrylate and TBA butyrate when compared with that of the widely-used TBA bromide. The slopes on pressure-temperature plane suggest differences in the incorporation of CH4 and CO2 in these hydrates. Characterization of the hydrate phases by X-ray diffraction analyses supports this mechanism. However, it is necessary to further understand the complicated gas incorporation in semiclathrate hydrate structures that are handled by ionic guest substances and the guest gas itself. (C) 2017 Elsevier B.V. All rights reserved.