The synergistic interaction between alginate and pectin was systematically investigated using samples of different chemical compositions. Pectin samples with high and low degrees of esterification (DE) and amidated pectin (LA) were mixed with alginate of high and low M/G (mannuronic acid/guluronic acid) ratio. The microstructure of the gels was characterised by TEM (transmission electron microscopy) and the rheological properties by dynamic oscillatory measurements. The TEM images of the mixed gels revealed a coarse, strand-like network with pores in the range of microns, independent of the ratio and the composition of the samples. A comparison with the microstructure of a pure pectin gel showed that the pectin network was composed of thinner strands and smaller pore sizes than the mixed network. The strongest synergism was found between alginate with low M/G ratio and pectin with a high DE. These gels show the highest G? (storage modulus) and the fastest kinetics of gel formation. Lower G? and slower kinetics were found for gels based on alginate with a high M/G ratio and pectin with a low DE, or LA pectin. The nature of the pectin sample affected the network density and the strand characteristics. In contrast, no influence was found of the alginate sample. Gels based on pectin with a high DE showed a dense network composed of highly branched strands, whereas the LA-pectin based gels showed a sparse, open network, composed of long, straight strands. A relation close to 1:1 for low-G alginate and pectin with a high DE resulted in gels with the highest G?. In contrast, for LA-pectin based gels, the highest G? was found for mixtures of alginate dominant ratios. For the overall network properties, the homogeneity in the microstructure decreased with alginate content, independent of the pectin sample. © 2003 Elsevier Science Ltd. All rights reserved.