The interaction of Cu2+ ions with the homopolymer poly(styrene sulfonic acid) (PSSH), as well as with the copolymers of maleic acid (MAc) with styrene sulfonic acid (SSH) or vinyl acetate (VAc), was investigated in dilute aqueous solution through turbidimetry, potentiometry, viscometry, and spectrophotometry in the visible region. Cu2+ ions were introduced either through neutralization with Cu(OH)2 of the acid form of the (co)polymers (PSSH, P(SSH‐co‐MAc) and P(VAc‐co‐MAc)) or through mixing of the sodium salt form of the (co)polymers (PSSNa, P(SSNa‐co‐MANa) and P(VAc‐co‐MANa)) with CuSO4. Turbidimetry, potentiometry, and spectrophotometry revealed that the first carboxylic group of MAc or both carboxylate groups of MANa are involved in the complexation with Cu2+ ions when neutralization with Cu(OH)2 or mixing with CuSO4 are applied, respectively. The increased values of the reduced viscosity observed mainly at the first stages of neutralization of P(VAc‐co‐MAc) with Cu(OH)2 indicate that interchain polymer‐Cu2+ complexation takes possibly place. Finally, the spectrophotometric behavior observed upon neutralization of P(SSH‐co‐MAc) with Cu(OH)2 or mixing of P(SSNa‐co‐MANa) with CuSO4 revealed that the strength of counterion binding by the sulfonate groups is, in fact, comparable with the complexation of Cu2+ ions with the carboxylate groups of MAc. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1149–1158, 2008