The invention relates to an air-cooled hardened steel plate with ultra-high strength, high toughness and an ultra-fine structure and a preparation process of the air-cooled hardened steel plate. The air-cooled hardened steel plate comprises the following components in percentage by mass: less than or equal to 0.08% of C, 0.1-0.35% of Si, 0.2-0.8% of Mn, 10-15% of Cr, 2.0-3.0% of W, 2.0-3.0% of Co,0.1-0.3% of V, 0.025-0.08% of Nb, 0.03-0.06% of N, 0.05-0.1% of Ta, 0.02-0.06% of Nd, less than or equal to 0.0005% of B and the balance of Fe and inevitable impurities. The preparation process comprises the steps of smelting, hot working treatment, secondary intermediate annealing treatment, medium-temperature strong deformation heat treatment and low-temperature aging treatment. Structural regulation and control are conducted through conventional equipment and production process, the martensite structure can be refined to the nanoscale, furthermore, a large number of nano-particles are separated out and distributed in a matrix in a dispersed mode, and the comprehensive performance of the low-carbon martensite steel plate is remarkably improved. Compared with the prior art, the preparedmaterial has ultrahigh strength, high toughness, good corrosion resistance, oxidation resistance, heat resistance and low-temperature performance. The preparation process is simple, industrial large-scale production is facilitated, production cost is low, production efficiency is high, and the product application range is wide.