The invention discloses an oxygen-enriched combustion system based on novel chemical chain oxygen production. The oxygen-enriched combustion system mainly comprises an air compressor, an air preheater, a first reactor, a second reactor, a first heating device, a second heating device, a boiler and an acting device, wherein an inlet of the air compressor communicates with an air supply pipeline, anoutlet of the air compressor communicates with a first inlet of a first four-way valve through the air preheater, a first outlet of the first four-way valve communicates with an inlet of the first reactor, a second outlet of the first four-way valve communicates with an inlet of the second reactor, and oxygen-carrying bodies are arranged in the first reactor and the second reactor respectively. The invention further discloses an oxygen-enriched combustion method based on the novel chemical chain oxygen generation. The oxygen-enriched combustion system has the beneficial effects that the air compressor is used for pressurizing and heating the air entering the reactors, oxygen absorption reaction occurs under the condition that the oxygen-carrying bodies in the reactors is higher than the oxygen-releasing temperature of the oxygen-carrying bodies, the heat absorbed by the oxygen-carrying bodies is accumulated by the oxygen-carrying bodies and inert carriers, and the heat of the oxygen-carrying bodies and the inert carriers are used for supplying self-release oxygen.