•analysis of mineralogical and organic composition of riverine suspended matter.•identification of key components governing freshwater floc formation.•phyllosilicates, iron oxides/(oxy)hydroxides & microbial exopolymers are key.•they enhance physicochemical surface heterogeneities and consequently flocculation.•floc formation mechanisms and dynamics in composition and morphology explained. Freshwater suspended particulate matter (SPM) plays an important role in many biogeochemical cycles and serves multiple ecosystem functions. Most SPM is present as complex floc-like aggregate structures composed of various minerals and organic matter from the molecular to the organism level. Flocs provide habitat for microbes and feed for larger organisms. They constitute microbial bioreactors, with prominent roles in carbon and inorganic nutrient cycles, and transport nutrients as well as pollutants, affecting sediments, inundation zones, and the ocean. Composition, structure, size, and concentration of SPM flocs are subject to high spatiotemporal variability. Floc formation processes and compositional or morphological dynamics can be established around three functional components: phyllosilicates, iron oxides/(oxy)hydroxides (FeOx), and microbial extracellular polymeric substances (EPS). These components and their interactions increase heterogeneity in surface properties, enhancing flocculation. Phyllosilicates exhibit intrinsic heterogeneities in surface charge and hydrophobicity. They are preferential substrates for precipitation or attachment of reactive FeOx. FeOx form patchy coatings on minerals, especially on phyllosilicates, which increase surface charge heterogeneities. Both, phyllosilicates and FeOx strongly adsorb natural organic matter (NOM), preferentially certain EPS. EPS comprise various substances with heterogeneous properties that make them a sticky mixture, enhancing flocculation. Microbial metabolism, and thus EPS release, is supported by the high adsorption capacity and favorable nutrient composition of phyllosilicates, and FeOx supply essential Fe. Display omitted