The preparation by electrospraying of a bilayer film formed by a pectin layer (hydrophilic, polar) and a zein layer (hydrophobic, nonpolar), is a difficult task that has not yet been reported. Herein, the feasibility of producing films by electrostatic atomization was studied, as well as the changes in the superficial and physicochemical characteristics of the bilayer film. Results showed that it is possible to produce a flexible and yellow bilayer film (101.07 ± 8.11 μm) with a continuous surface structure and a well‐defined interface, without chemical interactions between both layers nor antimicrobial activity. This study is one of the first to show that the electrospraying technique can be used to generate biodegradable bilayer films using hydrophilic/hydrophobic biopolymer solutions. A pectin‐zein bilayer film, using a novel technique (electrospraying) for more ecological alternatives to reduce the use of plastics, was prepared. The electrospraying technique proved to produce an easy to be degraded multilayer films, make of two biopolymers with different polarity and solubility characteristics. These findings could be the basis for the fabrication of multilayer films, added or not with other materials, to give many different applications.