The thermoreversible gelation of poly[hexyl isocyanate] (PHIC), a rather stiff polymer, has been studied in two closely-related solvents of the alcane series, namely heptane and octane. Temperature-concentrations phase diagrams have been established for both systems. The occurrence of polymer-solvent compound is suggested in heptane but not in octane. This conclusion receives further support from neutron diffraction investigations through the use of the isotopic labelling technique. Finally, it is observed that the morphology is also affected by the solvent type although still displaying a fibrillar network structure. (c) 2006 Elsevier Ltd. All rights reserved.