Coatings based on polyaniline (PANI) can improve the resistance of steel against corrosion. In this work, the preparation of stable suspensions of colloidal PANI-SiO2 particles, suitable for obtaining of composite anticorrosive coating on steel, is described. Electrokinetic data as a function of pH are presented, showing that the zeta potentials of the PANI-SiO2 particles are governed primarily by the charged groups at the silica oxide surface. Electrosteric stabilization of the PANI-SiO2 particles’ suspension against aggregation is realized at pH>5.5 (EB form of PANI) by adsorption of positively charged polyelectrolyte molecules onto negatively charged PANI-SiO2 particles. The PANI-SiO2 particles are incorporated by electrodeposition into the metal matrix of zinc in order to obtain composite (hybrid) coatings. The latter are aimed to ensure sacrificial protection of steel mainly in aggressive media leading to local corrosion damages. The surface morphology of the composite zinc coatings is investigated with SEM. The influence of PANI-SiO2 particles on the cathodic and anodic processes occurring in the starting electrolyte for obtaining of the coatings is followed with cyclic voltammetry. The electrochemical and corrosion behavior is evaluated with potentiodynamic polarization curves and polarization resistance measurements. The beneficial effect of the stabilized PANI-SiO2 particles for the increased protective ability of the composites is commented and discussed.