Three new emitting compounds of 5P-VCB, 5P-VAn and 5P-VPy for OLED based on hexaphenylbenzene moiety were synthesized. Physical properties by the change of the substitution groups of the synthesized materials were systematically examined. Photoluminescence spectrum of the synthesized materials showed maximum emitting wavelengths of about 420 approximate to 487nm in solution state and 452 approximate to 488nm in film state, indicating blue emission color. OLED devices were fabricated by the synthesized compounds using vacuum deposition process as an emitting layer. Current efficiencies and CIE values of 5P-VCB, 5P-VAn and 5P-VPy were 1.76, 0.38 and 7.91 cd/A and (0.15, 0.07), (0.20, 0.31) and (0.20, 0.36), respectively.