The addition of boron (B) to steels suppresses the austenite to ferrite phase transformation dramatically, thus increasing their hardenability. It achieves this through grain boundary (GB) segregation at the austenitic GBs that delays the ferrite nucleation. Though the effects of B segregation on hardenability have long been known, the mechanisms of B segregation and how exactly B suppresses the ferrite nucleation remain elusive. We designed a B-containing low-C steel to study the B segregation and precipitation behavior. We conducted heat treatments with different austenitization temperatures and cooling rates. Site-specific atom probe tomography, complemented by high-resolution secondary ion mass spectrometry reveals B segregation at prior austenite grain boundaries (PAGBs) along with carbo-boride precipitation. The B segregation mechanisms are discussed in detail based on these observations considering their dependence on austenitization temperature and cooling rate. Furthermore, we analyzed the impact of GB energy reduction through nucleation kinetics calculations. From our analysis, we conclude that the reduction in GB energy affects the grain corner and grain edge nucleation substantially. However, the retarding effects of carbo-boride precipitation on ferrite nucleation cannot be completely excluded. We provide a detailed account of the possibilities of how B-containing precipitates may be suppressing ferrite nucleation.