Stoichiometric ionically bonded side-chain polymer complexes of poly(styrene sulfonate) and quaternary ammonium-functionalised azo-containing surfactomesogens were exposed to controlled humidity atmosphere, to organic non-solvents (acetone, THF, ethyl acetate) and to a good solvent (DMF) for the complex. This modifies or increases the packing order, and includes induction of a crystal-like lamellar structure that is amenable to photoisotropisation. The molecular packing order influences photoinduced birefringence relaxation. Conditions for frozen-in morphologies are discussed in the light of higher temperature data. The observed diversity of phase changes upon solvent exposure is comparable to what is observed in surfactant–polyelectrolyte complexes.