There are several techniques useful for preparing biodegradable chitosan-based polymer particles. The preparation of microparticles of uniform size with controlled morphology is still a challenge. Some of the most commonly used methods for obtaining microparticles are methods based on the preparation of emulsions, the electrospraying process and the spray drying method. Due to simplicity and high efficiency, electrospraying process was used in this work. This work investigates the influence of the addition of copper (Cu2+) and zinc (Zn2+) ions on the size, shape and microstructure of microparticles of the bimetallic ion–chitosan complex (Cu2+/Zn2+‒CHT85) obtained by electrospraying. The morphology of the Cu2+/Zn2+‒CHT85 microspheres was investigated by a scanning electron microscope, which confirmed the sphericity of the microparticles observed using an optical microscope. The size and distribution of the particles depends on the concentration of metal ions, and estimated diameter of microspheres Cu/Zn0.5‒CHT85 and Cu/Zn5‒CHT85 was 80 ± 22 μm and 107 ± 32 μm, respectively. The identification of dry microspheres was carried out by Fourier infrared spectroscopy (ATR-FTIR) which indicated the absence of new absorption bands and slight changes in the intensities and wave numbers of the absorption bands of amino and hydroxyl groups, amide I and amide II. These changes could indicate that copper and zinc ions are coordinated by the nitrogen and oxygen atoms in the polymer. Chitosan-based microspheres can be successfully obtained by electrospraying method.