The diffusion layer and melt of silicon-boron are respectively obtained after quenched in water at 1300 oC by using metallurgical grade silicon (MG-Si) powder and amorphous boron powder. The phase equilibria for boron in MG-Si have been investigated by using X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS). The back scattered electron (BSE) image of diffusion layer displays the intermediate phase SiB4 in silicon-boron phase band, and the XRD results also indicate that SiB4 exists in silicon-boron diffusion layer at 1300 oC. It is inferred that the intermediate phase SiB4 is formed by the reaction (Si) + SiB6 ↔ SiB4 according to the equilibrium composition of Si/B=4/1 as quantified by Energy Dispersive Spectroscopy.