Abstract: MnO_x thin films on various types of substrates (glass, quartz, alumina, and Pt/Al₂O₃/Pt) were prepared by a combination of the sol–gel method and pen plotter printing, using the hydrolytically active heteroligand complex [Mn(C₅H₇O₂)_{2 –x}(C₄H₉O)_x] as the precursor. The effect of synthesis parameters and printing modes on the microstructure, optical and electrophysical properties of the manufactured planar nanomaterials was studied. The electron work function of the MnO_x film surface was assessed by Kelvin probe force microscopy (KPFM). Impedance spectroscopy was used to determine the temperature-dependent electrical conductivity of the prepared films in the temperature range 325–500°С. The proposed synthetic method and printing technology show promise for the formation of thin-film manganese oxide nanostructures for supercapacitor electrodes and optical devices.