Ni brazing alloy coating on soft metal substrate has been made extensively with different hard-facing processes. Among various hard-facing processes, hot-dipping has rarely been investigated as an inexpensive technique. In this study, thick Ni-Cr-Si-B-Fe alloy coating (>3 mm) has been made successfully on the plain carbon steel substrate with hot-dipping process. Microstructure and phase identification have been made to the coating with SEM and XRD. It was found that the Ni brazing alloy coating has good binding steel substrate with defect free. Four regions across the thickness of Ni brazing alloy coating, due to solidification conditions upon hot-dipping, have been identified with distinguished microstructure. The main phases of the coating include hard phases of CrB, Fe2B, and Cr23C6 dispersed in g(Fe,Ni) matrix.