Variable-temperature H-2 NMR investigations were been carried out to study the molecular behavior of perdeuterated benzene in the inclusion compound with tris(1,2-dioxyphenyl)cyclotriphosphazene. A comprehensive variable-temperature H-2 NMR study is presented comprising line shape studies and spin-spin and spin-lattice relaxation experiments. The experimental data clearly indicate the presence of highly mobile guest species at room temperature. Sample cooling gives rise to characteristic line shape effects at around 140 K that can be attributed to a slowing of the rotational motion (nondegenerate three-fold jump processes) of the guest species about the cyclophosphazene channel long axis. The rotation of the benzene molecules about their molecular C-6 axes can be followed to even lower temperatures (similar to40 K). A quantitative analysis of the experimental data is achieved by appropriate computer simulations taking into account various motions of the benzene guests. The derived activation energies for the overall rotations are rather small with values of 5.4 +/- 0.3 and 4.2 +/- 0.1 kJ/mol for motion about the channel long axis and 2.1 +/- 0.1 kJ/mol for rotation about the molecular C-6 axis. However, these values are larger than those reported earlier for aliphatic cyclic guests, which directly points to stronger nonbonded guest-host interactions in the present systems. The guest ordering is described by an almost perpendicular orientation of the benzene C-6 axis with respect to the cyclophosphazene channel long axis. The ordering of the benzene guests, which is reduced by fast overall fluctuations of small amplitude, is substantially higher than that observed in related systems, which again can be attributed to the aforementioned guest-host interactions.