Electrochemical energy storage systems have a wide range of commercial applications. They keep energy and power even at temperatures up to +60 °C. However, the capacity and power of such energy storage systems reduce sharply at negative temperatures due to the difficulty of counterion injection into the electrode material. The application of organic electrode materials based on salen-type polymers is a prospective approach to the development of materials for low-temperature energy sources. Poly[Ni(CH3Salen)]–based electrode materials synthesized from different electrolytes were investigated by cyclic voltammetry, electrochemical impedance spectroscopy and quartz crystal microgravimetry at temperatures from −40 °C to 20 °C. By analyzing data obtained in various electrolyte solutions, it was shown that at subzero temperatures, the process of injection into the polymer film, together with slow diffusion within the film, predominantly limit the electrochemical performance of electrode materials based on poly[Ni(CH3Salen)]. It was shown that the deposition of the polymer from solutions with larger cations allow the enhancement of the charge transfer due to the formation of porous structures facilitating the counter-ion diffusion. © 2023 by the authors.