Acid soluble biopolymeric substances (SBP) were isolated from different urban biowastes comprised of a range of materials available from metropolitan areas. These biowastes provided products with a chemical nature and solubility properties changing over a wide range and, thus, allowed to assess the effect of the variability of the chemical nature on molecular conformation and surface activity in water solution. For this scope, the SBP were characterized for chemical composition and molecular weight (MW) by microanalysis, potentiometric titration, (13)C NMR spectroscopy, and size exclusion chromatography (SEC) coupled with an online multiangle light scattering (MALS) detector. These materials were found to have 67-463 kg mol(-1) MW and 6-53 polydispersity index and to contain carboxylic acid and phenol groups bonded to aromatic and aliphatic C chains. An empirical parameter (LH) was calculated for use as an index of the lipophilic/hydrophilic C atoms ratio. The products solubility properties in solvents of different polarity, surface activity, power to enhance the water solubility of hydrophobic compounds, and particle size in water solution were also investigated by measurements of the products partition coefficient between polyethylene glycol and water (KPEGW) and of air-water surface tension (γ), water-hexane interfacial tension (IFT), disperse red orange dye solubility (DS), and dynamic light scattering (DLS) versus added SBP concentration (Cs). The results indicate that LH correlates well with KPEGW and with the products surface activity properties. Both γ and DS are shown to depend on Cs, although in opposite ways, that is, higher Cs values yield lower γ and higher DS values. Both DS-Cs and γ-Cs plots showed a significant slope change at approximately the same 1.8-2.5 g L(-1) Cs value. This suggested a change of molecular conformation taking place at the above Cs values. Hydrodynamic diameter values for SBP in solution at Cs ≤ 10 g L(-1) were found to range from 130 to 300 nm, consistent with their macromolecular nature. The DLS coupled to the γ data were consistent with molecules at the water-air interphase and in the bulk water phase having different conformations, but not significantly different molecular sizes. Molecular aggregates more likely form at 50-100 g L(-1) Cs. The results confirm that urban biowastes are a sustainable source of biobased products that may have real commercial perspectives.