The invention discloses a steel for R4-grade mooring cables and a preparation method thereof. The steel comprises the following components in percentage by weight: 0.15-0.24% of C, 0.15-0.30% of Si, 1.2-1.60% of Mn, at most 0.025% of P, at most 0.025% of S, at most 0.02% of Cu, 0.8-1.3% of Cr, 0.70-1.30% of Ni, 0.2-0.50% of Mo, 0.02-0.05% of Al, at most 0.0050% of As, at most 0.0050% of Sb, at most 0.0050% of Sn, at most 0.0050% of N, at most 0.0020% of O, at most 0.0020% of H, and the balance of Fe and inevitable impurities. The preparation method comprises the following steps: molten iron desulfurization, converter smelting, argon blowing, LF (ladle furnace) refining, RH vacuum treatment, continuous casting, square billet heating, rolling, air cooling and nondestructive flaw detection. The steel for R4-grade mooring cables has the advantages of high strength, high toughness, low cost and corrosion resistance.