Studies that are focused on the design and development of biodegradable materials with promising physicochemical properties for industrial use have been of great importance. In this research, bilayer materials were developed using TPS monolayers assembled with monolayers sheets of amorphous polylactic acid (PLAa) and polycaprolactone (PCL). Potassium sorbate was evaluated as an interfacial adhesion material. Structural properties of the laminated materials (FTIR and SEM), behaviour with water (rate of water vapour transmission, solubility in water and moisture content) and biodegradation of the materials were evaluated. Physical and chemical interactions between the studied monolayers by the addition of potassium sorbate were found. The use of monolayer sheets of PLAa and PCL overcomes the disadvantages of the materials obtained from starch. A practical alternative was developed to obtain materials with better properties. Besides, the degradation time of TPS was evaluated and compared with other polymers. These laminated materials are a great alternative to the decrease in the use of conventional plastics and are applicable as packaging in the food industry.