Based on the theoretical analysis of the application of Three-Roller Milling (TRM) exfoliating technology in low-carbon carbon-containing refractories, graphite nanoplatelets (GNP) were obtained by exfoliating flake graphite (FG) in phenol formaldehyde resin (PF) via TRM in this study. The effects of the exfoliating times on the structure and morphology of the products were investigated. By using alcohol as the solvent, the product exfoliated from FG by TRM was soaked and washed by ultrasound to remove PF, followed by drying, and then characterized by XRD, SEM, TEM and particle size analysis. It was found that the original FG with 150 μm in size and several microns in thickness was constantly exfoliated. When the exfoliating times were increased gradually to 8 or even 16 times, GNPs were obtained with a size of 10-30 μm and a thickness of 30-100 nm. This technical ideal can be applied in low-carbon and ultra-low carbon refractory industries to reduce carbon content, as well as in resin based carbon fiber composites for aviation industry to improve resin strength.