Сombining the sol–gel method and pen plotter printing, using the hydrolytically active heteroligand complex [Co(C₅H₇O₂)_2-x(C₄H₉O)_x] as a component of a new functional ink, Co₃O₄ thin films were produced on the surface of substrates of various types. The influence of synthesis conditions and print modes on the microstructure, optical, electrophysical and sensor properties of planar nanomaterials was comprehensively studied. The optical band gap energies associated with charge transfer for transitions O^2-→Co³⁺ and O^2-→Co²⁺ of the obtained thin films were evaluated. Using Kelvin probe force microscopy and impedance spectroscopy, the electrophysical characteristics (the electronic work function of the film surface, the temperature dependence of electrical conductivity, and the activation energy of electrical conductivity) of the obtained Co₃O₄ films were determined. The sensitivity of printed cobalt(II, III) oxide thin films with respect to various gases (Н₂, СН₄, СО and NO₂) was studied. It was established that the obtained samples demonstrated the highest sensor response when detecting CO and NO₂ in the operating temperature range of 150–200°С. The prospects of the proposed synthesis method and printing technology when forming Co₃O₄ thin-film nanostructures to create electrodes of supercapacitors and receptor components of resistive CO and NO₂ gas sensors were shown.