Poly(3,4-ethylenedioxythiophene)–polystyrene sulfonate (PEDOT:PSS) conjugated polymer blend and a cationic poly(3-hexylthiophene) (P3HT)-based conjugated polyelectrolyte incorporating imidazolium ionic side groups were first adsorbed as monolayer on inorganic colloidal particles. At the plateau of adsorption isotherm, adsorbed amount of PEDOT:PSS on alumina particles appears lower than the adsorbed amount of P3HT on silica particles. Both polyelectrolytes strongly modify the surface charge of particles as reveals by zeta potential variation. Functionalized particles were then assembled using Layer-by-Layer method in order to prepare (PDDA/Al2O3-PEDOT:PSS)n and (SiO2-P3HT/PEDOT:PSS)n conductive multilayer film. Thicker PDDA/Al2O3-PEDOT:PSS films were elaborated when a drying step was added during the LbL build-up. The same effect was observed when composite particle concentration was increased from 1 to 10 g.L−1. Electrical behavior of film was completely modified in comparison with PDDA/PEDOT:PSS assembly. After heating at 150 °C, no conductivity was detected due to microcracks visible on SEM images. For SiO2-P3HT/PEDOT:PSS assembly, thickness is higher than for PDDA/Al2O3-PEDOT:PSS assembly using the same experimental procedure. However, even if two conductive polyelectrolytes were embedded into the film, conductivity was too low at 30 °C to be measured by van der Pauw technique probably due to the cracking of the film induced by incorporation of silica particles.