This work is devoted to the studying of effects of La2NiO4 doping with alkaline-earth elements: Ca, Sr, and Ba (at an amount of 15 mol %) on its structural, electrical, and electrochemical properties. The effects of the alkaline-earth element nature, introduction of the Ce0.8Sm0.2O1.9-electrolyte (SDC) component to the functional layer, and the presence of collecting film onto electrochemical activity of the electrodes contacting the Ce0.8Sm0.2O1.9-electrolyte are examined. The doping was found to increase the La2NiO4 full conductivity due to increase in the hole conductivity. The maximal conductivity (at the sample density of 86–89%) was obtained for the Ca-doped composition: 85 S/сm at 700°C, as compared with 65 S/сm for undoped La2NiO4. at the same time, the doping was found to deteriorate the electrodes’ electrochemical activity which is likely to be due to loss of interstitial oxygen as a result of the doping. The using of composite electrodes allows increasing polarization conductivity markedly. For instance, at 700°С the conductivity of La2NiO4 is 0.25 S/сm2; of its based composite, 0.67 S/сm2.