Stable van der Waals-bonded C 60 /benzene solvates were prepared using a novel crystallization technique. Solid-state NMR measurements on highly crystalline solvate under liquid benzene show that there is very little interaction between benzene and the C 60 molecules and that the rotation of C 60 at room temperature is not hindered. The magnetization transfer between benzene protons and local C 60 molecules is highly inefficient. Three benzene species have been found in the solvate: two, nearly freely mobile, in wide and narrow porous structures, and the third constrained by C 60 molecules in lattice defects. Premelting of deuterated benzene within the C 60 solvate has been observed at T m -10.5 K.