This study aims to investigate the mechanical properties of corroded structural steel under monotonic tensile loading. First, structural steel coupons with various corrosion degrees were produced by electrolytic accelerated corrosion using a particular etchant solution proposed by the authors. Second, the corroded morphologies of the specimens were observed through a morphology scanner; then, the mechanical properties were examined by monotonic tensile loading tests. An analytical model on the relationship between mass loss and surface morphology with the mechanical properties of corroded structural steel was established. Finally, a numerical simulation method was proposed on the mechanical behaviour of corroded structural steel based on random rough surface theory. The finite element was consistent with experimental tests, which indicates the feasibility and accuracy of the proposed simulation method.