AbstractA large amount of metallurgical solid waste accumulation poses a serious threat to the environment. Study on synergistic reinforcement of synthetic process of metallurgical solid waste‐based ceramics with fly ash is of great significance in reducing environmental pollution and resource utilization. A metallurgical solid waste‐based ceramic used as building ceramic was developed with the erosion part of used MgO–C bricks and fly ash as main raw materials, and the amount of solid waste added to the prepared ceramics was at least 60 wt% and up to 90 wt%. The effects of fly ash content and sintering temperature on the crystalline phase transitions, morphologies, and the main physical and mechanical properties of ceramics were investigated by X‐ray diffraction, scanning electron microscopy, and mechanical testing. The results show that the obtained ceramics presented maximum bending strength and minimum water absorption, 80.14 MPa and 5.04%, respectively, when the raw material proportions were the erosion part of used refractories accounted for 60 wt%, fly ash 20 wt%, pyrophyllite 10 wt%, and quartz sands 10 wt%, and the process parameters were the sintering temperature 1150°C, sintering time 120 min, and molding pressure 15 MPa.