The present study explores the potential use of asymmetrical flow field flow fractionation (aFlFFF) with a multidetection system for the study of metal–alginate interactions. aFlFFF, coupled on-line to a differential refractive index and seven angle laser light scattering detectors was used to provide information on the alginate size distributions. In parallel, the metal distributions of metal–alginate complexes were probed by aFlFFF–high resolution inductively coupled plasma-mass spectrometry. Average values and continuous distributions of molar masses, radiuses of gyration and hydrodynamic radiuses, which are critical for understanding the role of alginates as carriers of metal pollutants, were evaluated in presence of Pb or Cd and compared with those in metal-free solutions of alginate. The values of number average and weight average molar mass, weight average radius of gyration and shape factor for alginate were 150 and 188 kg mol−1, 53 nm and 1.7, respectively. Alginate molar mass and radius of gyration distributions were slightly shifted to higher values by the addition of micromolar concentrations of Pb or Cd. The alginate size distribution in the presence of Cd was similar to the alginate-alone control, whereas in the presence of Pb the size distribution was broader with a shift of the maximum toward higher molar masses.