The formation of complex coacervates between chitosan and alginate was evaluated during microparticles formation. Mass ratio between polyelectrolytes and calcium chloride concentration were determinated by conductimetric analysis and by calcium ions quantification, respectively. Inert microparticles were prepared using a complex coacervation method in W/O emulsion and morphological analyses of microparticles were carried out. This method enabled the production of spherical particles, with slightly rough surface and narrow size distribution with maximal diameter of 10 μm.