In this paper, mullite porous ceramics were prepared by dry compression molding method using construction waste as main raw material, alumina as aluminum source, aluminum fluoride as whisker catalyst, boron oxide, cerium oxide and molybdenum trioxide as sintering aids, and corn starch as pore forming additive. The effects of cerium oxide and molybdenum trioxide contents on the structure and physicochemical properties of the mullite porous ceramics were investigated, and the ceramics with the best performance were loaded with TiO2/Ce-TiO2 for photocatalytic degradation of simulated printing and dyeing wastewater. The results show that, in terms of mass fraction, when the content of cerium oxide is 4% and the content of molybdenum trioxide is 1%, the flexural strength of porous ceramics is 8.69 MPa, and the open porosity is 64.25%. Loading with 0.05 g Ce-TiO2 and mixing with 1.2 mmol/L PMS, the degradation rate of the methylene blue solution reaches 96.62% after 120 min of irradiation with LED visible light at power of 18 W and wavelength of 420~430 nm.