Chitosan (CH) films were prepared with/without glycerol as a plasticizer and coated with polycaprolactone (PCL) and cycloolefin copolymer (COC) to form bilayer films. The effect of the second layer coating on the physicomechanical properties of CH films was determined. The adhesion of PCL and COC solutions, when coated on CH film, was investigated by contact angle measurement. The contact angle of PCL film solutions was lower than COC film solutions (P <0.05). Scanning electron microscopy analysis revealed better compatibility between CH and PCL, while a phase separation was observed for CH/COC bilayers. Bilayers showed higher resistance to water when compared to neat CH film samples (P <0.05), while a reduction was found in tensile properties for bilayer films. Bilayer films had similar transmittance values with monolayer films (P >0.05). The physicomechanical properties of CH films significantly influenced by the addition of glycerol and application of the second layer.