Structure-H hydrate has been highlighted due to its higher gas storage capacity and favorable thermal stability. Here, we introduce a new structure-H hydrate former, tert-butyl nitrite, and identify it through spectroscopic analysis. The hydrate structure and guest distribution were examined by using powder X-ray diffraction, Raman spectroscopy, and solid-state high-power decoupling (13)C NMR spectroscopy. The phase equilibria (L(w) + H + L(g) + V) of tert-butyl nitrite + CH(4) hydrate were measured at pressures from (3 to 4.5) MPa and at temperatures from (277 to 282) K. We also investigated the kinetic behavior of this new high-polarity hydrate former.