The present study is concerned with the influence of niobium(Nb) addition and austenitizing temperature on the hardenability of low-carbon boron steels. The steel specimens were austenitized at different temperatures and cooled with different cooling rates using dilatometry; their microstructures and hardness were analyzed to estimate the hardenability. The addition of Nb hardly affected the transformation start and finish temperatures at lower austenitizing temperatures, whereas it significantly decreased the transformation finish temperature at higher austenitizing temperatures. This could be explained by the non-equilibrium segregation mechanism of boron atoms. When the Nb-added boron steel specimens were austenitized at higher temperatures, it is possible that Nb and carbon atoms present in the austenite phase retarded the diffusion of carbon towards the austenite grain boundaries during cooling due to the formation of NbC precipitate and Nb-C clusters, thus preventing the precipitation of M23(C,B)6 along the austenite grain boundaries and thereby improving the hardenability of the boron steels. As a result, because it considerably decreases the transformation finish temperature and prohibits the nucleation of proeutectoid ferrite even at the slow cooling rate of 3 oC/s, irrespective of the austenitizing temperature, the addition of 0.05 wt.% Nb had nearly the same hardenability-enhancing effect as did the addition of 0.2 wt.% Mo.