Methane storage as SNG (solidified natural gas) in the form of clathrate hydrates is an emerging, economically feasible and environmentally benign technology for large scale storage. Mixed tetrahydrofuran (THF)-methane (CH4) hydrates offer a paradigm shift to milder storage conditions and faster hydrate formation kinetics, providing a promising scenario to scale up the SNG technology. In this work, we synthesize mixed THF-CH4 hydrates in a high pressure microdifferential scanning calorimeter (HP μ-DSC) to elucidate the two-step hydrate formation mechanism of mixed THF-CH4 hydrate identifying the synergism between THF and CH4. Heat flow change during hydrate formation and dissociation of mixed THF-CH4 hydrates formed in the presence of 5.56 mol % THF (stoichiometric composition) were monitored. The two step-mechanism of mixed THF-CH4 hydrate formation was further confirmed by the pressure-temperature profile and visual observations with a sample volume scale-up of about 350 times that of μ-DSC experiments. (Figure Presented). © 2016 American Chemical Society.