Effects of Cu and B on effective grain size and low-temperature toughness of thermo-mechanically processed high-strength bainitic steels were investigated in this study. The microstructure of the steel specimens was analyzed using optical, scanning, and transmission electron microscopy; their effective grain size was also characterized by electron back-scattered diffraction. To evaluate the strength and low-temperature toughness, tensile and Charpy impact tests were carried out. The specimens were composed of various low-temperature transformation products such as granular bainite (GB), degenerated upper bainite (DUB), lower bainite (LB), and lath marteniste (LM), dependent on the addition of Cu and B. The addition of Cu slightly increased the yield and tensile strength, but substantially deteriorated the low-temperature toughness because of the higher volume fraction of DUB with a large effective grain size. The specimen containing both Cu and B had the highest strength, but showed worse low-temperature toughness of higher ductile-brittle transition temperature (DBTT) and lower absorbed energy because it mostly consisted of LB and LM. In the B-added specimen, on the other hand, it was possible to obtain the best combination of high strength and good low-temperature toughness by decreasing the overall effective grain size via the appropriate formation of different low-temperature transformation products containing GB, DUB, and LB/LM.