Diamond crystallization was carried out with CH4N2S additive in the FeNiCo-C system at pressure 6.0 GPa and temperature ranging from 1290 °C to 1300 °C. The crystallization qualities of the synthetic crystals were characterized by Raman spectra and the Raman peaks located at 1331 cm-1. Fourier transform infrared (FTIR) results showed that the hydrogen-related absorption peak of the as-grown diamond was at 2920 cm-1, respectively. Interestingly, A-center nitrogen was observed in the obtained diamond and the characteristic absorption peaks located at 1095 cm-1 and 1282 cm-1. Especially, the absorption peak at 1426 cm-1 attributing to the aggregation B-center nitrogen defect was distinctly found when the CH4N2S content reached 0.3 mg in the synthesis system, which was extremely rare in synthetic diamond. Furthermore, optical color centers in the synthesized crystals were investigated by photoluminescence (PL).