In order to study the thermal properties of new type environment-friendly binary hydrate for cold storage in air-conditioning system, tests have been carried out by DSC comprehensively on the phase-change temperature and fusion heat of TBAB hydrate, THF hydrate, and TBAB–THF hydrate mixture. The results show a good trend that TBAB–THF hydrate has the superiority for more proper phase-change temperature and increased fusion heat. A broader and more developed view is that adding appropriate amount of hydrate with lower phase-change temperature to hydrate with higher one can make the hydrate mixture more suitable for cold storage (especially for 278–281 K); some hydrates with lower phase-change temperature can even make the fusion heat of mixture hydrate increased greatly. Several new environmental working pairs for binary gas hydrates have been listed to help to promote the application.