The binding of a photosurfactant, 4-butyl-azobenzene-4'-oxyethyltrimethyl ammonium bromide (BZTABr), to a linear polymer, sodium poly(2-acrylamide-2-methylpropane sulfonate) (PAMPS), has been studied by using a surfactant selective electrode. The photosurfactant undergoes a trans-cis transition on UV/vis irradiation. The binding behavior changes by varying the composition of the trans and cis forms in the solution. The ideal mixing-ideal cooperative binding model we had proposed previously for the binding of binary surfactants was applied to successfully predict the binding isotherms and the critical aggregation concentrations of the present systems. The binding of a trans-cis mixture of BZTABr to a polymer is analogous to the ideal mixed micelle formation. A sort of synergetic effect was found in the binding process. Copyright 1999 Academic Press.