The invention discloses high-strength, high-toughness, high-heat conductivity and high-impermeability large-volume concrete and a preparation method thereof. The high-strength, high-toughness, high-heat conductivity and high-impermeability large-volume concrete comprises cement, fly ash, silicon powder, steel slag powder, boron nitride, graphene oxide flake powder, sand, gravel, high-strength polyvinyl alcohol fiber, a polycarboxylic acid water reducing agent, a dispersion activator, a modified graphene oxide dispersion and water. The obtained concrete has the initial and 28-day-old heat conductivity of 6.26-7.53W/(m.K) and 9.58-12.73W/(m.K) respectively and has the capability of dispersing and conducting cement hydration heat and resisting temperature cracks caused by environment temperature change; 28-day-old concrete has the compressive strength of 87.6-116.7MPa, the rupture strength of 17.6-19.5MPa, the splitting tensile strength of 11.7-12.6MPa, the bending tensile strength of 12.4-13.8MPa and the bending tensile modulus of 45.7-52.5GPa; the water permeability resistance, the chloride ion permeability resistance, the freeze-thaw resistance and the carbonation resistance reachthe highest levels; and the prepared concrete has good social and economic benefits.