In this study, we introduce a new structure-II hydrate former, 2-methylpropane-2-peroxol (tert-butyl hydroperoxide, TBHP), and identify the structure and guest distributions through spectroscopic tools including high-resolution powder diffraction (HRPD), C-13 solid-state NMR, and Raman spectroscopy. Here, the (H + L + V) phase equilibrium data of (TBHP + X) hydrates (X = CH4, N-2, and O-2) were measured at (3.3 to 7.56) MPa and (282.2 to 288.5) K for CH4, (4.0 to 8.5) MPa and (271.6 to 277.5) K for N-2, and (4.0 to 8.6) MPa and (273.8 to 279.6) K for O-2. The (TBHP + X) hydrate phase equilibria showed that the addition of TBHP increased the structural stability with lower hydrate dissociation pressures when compared with those of pure CH4, N-2, and O-2 hydrates. However, we noticed that the TBHP did not promote hydrate formation conditions as effectively as tetrahydrofuran.