In this study, the effect of subsequent heat treatment applied to high-strength low-alloy steel (HSLA) on the structure–property relationships was investigated. Tempering and intercritical annealing processes are introduced to elucidate the influence of subsequent heat treatment on mechanical properties of direct-quenched Fe-0.06C-0.2Si-2.0Mn steel from a microstructural perspective. The tempering process results in a typical tempered martensite with uniformly dispersed cementite, whereas the intercritical annealing process forms a dual-phase microstructure composed of soft ferrite and hard martensite for the direct-quenched steel. In the intercritical annealed steel, a number of mobile dislocations at the interphase (martensite/ferrite) boundary significantly decrease the yield strength, and the large difference in strength between ferrite and martensite enhances work hardening. Charpy V-notch impact test results indicate that the tempering and intercritical annealing processes improved the absorbed energy by more than 100 J compared to the direct-quenched steel at room temperature, and at −50 °C, the intercritically annealed steel exhibited the highest absorbed energy of approximately 140 J. Additionally, the high fraction of high-angle grain boundaries and fine grains of the intercritically annealed steel increase the resistance to cleavage crack propagation, thereby reducing the ductile-to-brittle transition temperature.