Abstract: Low-carbonization and high-performance improvement of carbon-containing refractories are recognized as key bottlenecks for the development of clean steel smelting technology. A novel strategy is proposed for the preparation of multilayer graphene (MLGs)-silicon carbide particle/whisker (SiC_p/SiC_w) composite reinforcements via three-roll milling exfoliation and catalytic in-situ conversion. Using expanded graphite (EG) as raw material and phenolic resin (PF) as medium, the effects of EG/PF mass ratio on the exfoliation efficiency of three-roll milling and the structural integrity of MLGs are investigated. With this MLGs/PF composite system as carbon source, in-situ catalytic synthesis of SiC_p/SiC_w is achieved by reacting with silicon powder at 1 400 ℃ under the action of nickel nitrate. Results show that the introduction of nickel nitrate is identified as the key factor driving the formation of SiC whiskers. During the reaction, parts of MLGs are retained and embedded into the SiC matrix as independent flake-like reinforcements. Meanwhile, the carbon network structure is optimized by the presence of MLGs, and the carbon yield of PF is increased to 50.9%. The complete pathway and reaction mechanism of nickel salt decomposition, reduction and catalytic Si-C exothermic reaction (peak temperature at 1 294 ℃) are clearly revealed by thermogravimetry-differential thermal analysis. The as-prepared MLGs-SiC_p-w composite can be applied as a two-dimensional carbon and ceramic phase to enhance the comprehensive performance of high-performance low-carbon refractories for clean steel production.