A double chambers boiler system with oxygen-enriched combustion is provided, relating to fields of thermal power engineering and mechanical manufacturing. The double chambers boiler system includes a boiler furnace subassembly and a combustion control subassembly. The boiler furnace subassembly includes a combustion chamber and a heat exchange chamber. The heat exchange chamber is arranged above the combustion chamber. A high temperature flue gas outlet is arranged between the combustion chamber and the heat exchange chamber. The combustion control subassembly includes a burner, a pure oxygen injector and a fuel injector. The double chambers boiler system with oxygen-enriched combustion is able to simultaneously solve problems of improving a combustion efficiency and reducing an emission concentration of NOx.