In this study, Si3N4−Si2N2O composite ceramics were prepared through a two‐step combination of the direct nitriding method and spark plasma sintering method with diamond‐wire saw silicon waste in the photovoltaic industry as raw material. The whole holding time at the constant temperature of the preparing process only lasts 35 min, in which the nitriding time only takes 30 min and the sintering time only takes 5 min. The effects of the Fe2O3 additive on the nitriding and sintering process were investigated in detail. The results show that the Fe2O3 additive accelerates the nitriding process by promoting the formation and diffusion of the gas phase and reducing the apparent activation energy of the reaction between the gas phase containing silicon and N2. Meanwhile, the Fe2O3 additive also promotes the sintering process by lowering the eutectic temperature of the SiO2−Al2O3 and the SiO2−Y2O3 binary system. The optimal technical parameters follow the nitriding temperature of 1400°C, the nitriding time of 30 min, the sintering temperature of 1800°C, and the sintering time of 5 min. The Si3N4−Si2N2O composite ceramic prepared under the above conditions exhibits good performance with an apparent porosity of 2.7%, Vickers hardness of 16.54 GPa, and fracture toughness of 4.1 MPa·m1/2.