The deoxidation, desulfurization, dephosphorization, microstructure, and mechanical properties of steels treated by barium-bearing alloys were investigated in laboratory and by industrial tests. The results show that barium takes part in the deoxidation reaction at the beginning of the experiments, generating oxide and sulfide compound inclusions, which easily float up from the molten steel, leading to the rapid reduction of total oxygen content to a very low level. The desulfurization and dephosphorization capabilities of calcium-bearing alloys increase with the addition of barium. The results of OM and SEM observations and mechanical property tests show that the structure of the steel treated by barium-bearing alloys is refined remarkably, the lamellar thickness of pearlitic structure decreases, and the pearlitic morphology shows clustering distribution. Less barium exists in steel substrate and the enrichment of barium-bearing precipitated phase mostly occurs in grain boundary and phase boundary, which can prevent the movement of grain boundary and dislocation during the heat treatment and the deformation processes. Therefore, the strength and toughness of barium-treated steels are improved by the effect of grain-boundary strengthening and nail-prick dislocation.