Boron-doped diamond single crystals were synthesized with Fe-Ni-C-B System catalysts which content of boron carbide (B4C) were different, and their crystallographic features were tested with electron probe microanalysis (EPMA), X-rays diffraction (XRD), Raman spectrum and field emission scanning electron microscopy (FESEM). The experimental results showed that doped boron in the diamond could result in the changes of its crystallographic features. There were different X-ray peak intensities in the different boron-doped diamond crystals, and the intensities were changed with the content of B4C in the catalysts. With the increase of boron content in the diamond, the boron atoms resulted in the change of growing rate in different crystalline face of the diamond. The quality of diamond synthesized with catalyst which contained 0.2 w.t.% boron carbide was worse than others.