Organosoluble polyelectrolyte-surfactant complexes (PSCs) based on cationic polymer – JR-400 and anionic surfactant – sodium salt of dodecylbenzenesulfonate (SDDBS) were isolated as a precipitate from polyelectrolyte/surfactant aqueous mixture. The reduced viscosity of JR-400/SDDBS in ethanol showed polyelectrolyte anomaly that was suppressed upon addition of 0.05N and 0.1N KBr. Light scattering measurements of JR-400/SDDBS in ethanol showed 4 peaks belonging to non-aggregated and aggregated polycomplex particles. The elemental composition and morphology of thin layers of polyelectrolyte-surfactant complexes deposited on SiO2 surface were evaluated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The height of PSC aggregates evaluated using AFM and Surface Enhanced Ellipsometry Contrast (SEEC) microscopy data is in good agreement and range within 10–50 nm. The XRD analysis revealed that PSCs have amorphous structure with a broad halo near 20 °. The contact angle measurements were used to demonstrate the hydrophobization of glass surface after the deposition of PSCs.