Herein, we reported the method of synthesis of sodium titanates using metal-ammonia solution and their photocatalytic activity for the gas-phase reduction of carbon dioxide under visible light. The results of physicochemical measurements showed that the obtained samples resemble multiphase systems containing Na2Ti4O9, Na4Ti5O12, and Na0.8Ti4O8 of cylindrical forms. They demonstrated perfect adsorption of visible light and improved activity in the investigated process. Display omitted •Intercalation of sodium into titanium dioxide was performed using a solution of sodium metal in liquid ammonia.•Multiphase systems containing sodium titanates of different stoichiometry (Na2Ti4O9, Na4Ti5O12, and Na0.8Ti4O8) were formed.•Localization of sodium ions in titanium dioxide depended on its initial concentration in liquid ammonia.•Absorption of visible light and photocatalytic activity of titanium dioxide were greatly improved.