Novel channel-like inclusion compounds were formed by tris(o-phenylenedioxy)spirocyclotriphosphazene (TPP) with linear hydrocarbons. The molecular characterization was performed by 13 C and 31 P solid-state NMR under magic angle spinning conditions. The hexagonal symmetry of the host was verified in the 31 P and 13 C MAS spectra and by X-ray powder diffraction patterns. The new inclusion compounds present congruent meltings, and the temperatures increase with chain length. These compounds provide the opportunity to observe hydrocarbons confined as isolated chains in the solid state at temperatures 200 K above their melting points. Furthermore, the aliphatic chains are in the unusual state of being surrounded by aromatic rings displaced parallel to the channel. This geometry was proved by a through-space 1.4 ppm upfield shift on the 13 C resonances of the guests, due to the aromatic ring current. The mobility at the chain ends and the propagation of the conformational defects within the guest molecules is discussed and a comparison made with alkanes in different inclusion compounds and bulk alkanes in the high-temperature modification. The formation of the inclusion compounds was also highlighted by throughspace transferring of magnetization from the hydrogens of the host matrix to the chain carbons of a deuterated guest under Hartmann-Hahn conditions.