1,2,4 trichlorobenzene (1,2,4-TrCB) is a persistent organic pollutant with chemical stability, biological toxicity, and durability, which has a significant adverse impact on the ecological environment and human health. In order to solve the pollution problem, bagasse cellulose is used as the basic framework and nano TiO2 is used as the photocatalyst to prepare composite carriers with excellent performance. Based on this, an intimate coupling of photocatalysis and biodegradation (ICPB) system combining photocatalysis and microorganisms is constructed. We use the combined technology for the first time to deal with the pollution problem of 1,2,4-TrCB. The biofilm in the composite carrier can decompose the photocatalytic products so that the removal rate of 1,2,4-TrCB is 68.01%, which is 14.81% higher than those of biodegradation or photocatalysis alone, and the mineralization rate is 50.30%, which is 11.50% higher than that of photocatalysis alone. The degradation pathways and mechanisms of 1,2,4-TrCB are explored, which provide a theoretical basis and potential application for the efficient degradation of 1,2,4-TrCB and other refractory organics by the ICPB system.