The Charpy impact resistance of monolithic high-strength and dissimilar structured steel was studied. A gas metal arc welding process was used to fabricate the structured steel by depositing a layer of austenitic stainless steel, followed by a layer of hardfacing material over the high-strength steel plate. ANSYS LS-DYNA^TM was used to simulate pendulum–striker impacts on steel Charpy samples. A Cowper–Symonds constitutive model was employed to capture the strain rate behavior. The corresponding material constitutive model parameters were obtained from the literature for the monolithic materials; an iterative numerical optimization method was used to couple the parameters of the structured steel simulation and experimental results. Numerical simulation results showed close agreement with experimental ones. Simulation is a valuable tool for explaining the fracture mechanism in the Charpy impact test and can be used to efficiently design parts made of structured steel that will be subjected to impacts or high-speed deformations.