A new route to the preparation of films and fibres of intractable rigid-rod molecules is described. Aromatic polyamide systems are prepared with varying levels of alkyl-based side-chain substitution, which leads to materials with good solubility in standard solvents such as tetrahydrofuran. The chemical structure and the physical properties of such materials may be transformed by cleavage of the solubilizing side-chains in the solid state. Films prepared in this manner are insoluble and intractable.