In this paper, Ag-Functionalized graphene electrocatalyst was prepared by simultaneous reduction of Ag[(NH3)(2)](+) and graphene oxide (GO) under the protection of Poly Diallydimethylammonium Chloride. The as-prepared, catalyst was utilized to enhance the catalytic activity toward oxygen reduction reaction (ORR) in energy-saving electrolysis of Na2CO3. The morphology characterization indicates that Ag nanoparticles uniformly disperse on the surface of reduced graphene oxide (RGO), and their average size is only about 5.7 mn. The electrochemical tests show that the as-prepared catalyst exhibits high electrocatlytic activity for ORR in alkaline media. Furthermore, when the catalyst is used for the oxygen reduction cathode (ORC) in the galvanostatic electrolysis of Na2CO3, the cell voltage can be reduced by 1.05 V, as compared with the conventional hydrogen evolution cathode (HEC) electrolysis. Correspondingly, up to 41.5% electrical energy consumption is saved at the same current density of 100 mA cm(-2).