The trivalent metal ion (M(III) = Cm, Eu)/polyacrylic acid (PAA) system was studied in the pH range between 3 and 5.5 for a molar PAA-to-metal ratio above 1. The interaction was studied for a wide range of PAA (0.05 mg L−1–50 g L−1) and metal ion concentrations (2×10−9–10−3 M). This work aimed at 3 goals (i) to determine the stoichiometry of M(III)–PAA complexes, (ii) to determine the number of complexed species and the local environment of the metal ion, and (iii) to quantify the reaction processes. Asymmetric flow-field-flow fractionation (AsFlFFF) coupled to ICP-MS evidenced that size distributions of Eu–PAA complexes and PAA were identical, suggesting that Eu bound to only one PAA chain. Time-resolved laser fluorescence spectroscopy (TRLFS) measurements performed with Eu and Cm showed a continuous shift of the spectra with increasing pH. The environment of complexed metal ions obviously changes with pH. Most probably, spectral variations arose from conformational changes within the M(III)–PAA complex due to pH variation. Complexation data describing the distribution of complexed and free metal ion were measured with Cm by TRLFS. They could be quantitatively described in the whole pH-range studied by considering the existence of only a single complexed species. This indicates that the slight changes in M(III) speciation with pH observed at the molecular level do not significantly affect the intrinsic binding constant. The interaction constant obtained from the modelling must be considered as a mean interaction constant.