AbstractIn this review paper the photoresponsiveness of photochromic macromolecules under different structural and environmental conditions is discussed with reference to results from the authors' laboratories. Polypeptides, in particular poly(L‐glutamic acid) and poly(L‐lysine), with spirobenzopyrane side chains show photoinduced conformational variations which are amplified by addition of organic acids or bases to hexafluoro‐2‐propanol (HFP) solutions. Thus combination of light and environment effects allows modulation of order–disorder conformational transitions.Such photoindiced conformational changes are not observed in the case of macromolecules with a hydrocarbon main chain and azobenzene or stilbene side chains, obtained by polymerization of acrylic monomers. However, even in these systems structural variations affect the dependence of optical properties on irradiation. Moreover, the combination of organic solvents and water shows that polymer solubility can be modulated