Recently, efforts have been made to apply the leak-before-break (LBB) design concept to the main steam line (MSL) piping in secondary systems of Korea standard nuclear power plants (KSNPs). In this study, the microstructures, mechanical properties, and consequential LBB margins of five candidate materials (SA335 Gr.P11/P22, SA508 Gr.3 Cl.2, SA508 Gr.3 Cl.1, and SA508 Gr.1A steels) were evaluated, and strong/weak points of candidate materials for applying MSL piping were analyzed through the comprehensive analysis including microstructure, mechanical properties, LBB margin, usage history, economics, and so on. SA508 Gr.1A steels, which has been used extensively as a piping material in NPPs and has a low fabrication cost, had a good combination of yield strength and fracture toughness. They had LBB margin of 1.11–1.21. SA508 Gr.3 Cl.1 steel had an excellent combination of yield strength and fracture toughness with an LBB margin of 1.64. SA508 Gr.3 Cl.2 steel had the highest LBB margin (1.84) because it had the highest strength; however, it had low fracture toughness and low upper shelf energy (USE). The effect of yield strength on the LBB margin was considerably higher than the effect of fracture toughness. SA508 Gr.3 Steels have high LBB margin owing to the high yield strength, but they have never been used for piping materials in NPPs before. SA335 Gr.P11 and P22 had the LBB margin of 1.1 and 1.23, respectively. However, the elongation and J-R fracture toughness of SA335 Gr.P11 and P22 decreased significantly at 286 °C owing to dynamic strain aging (DSA).