A prototype for the typical optical single-sideband(SSB) modulated radio-over-fiber (ROF) system was presented by employing a phase-shifted superstructure Bragg grating. The grating has different transmission characteristics with different oblique angle. So, the different transmission peak could be obtained with different phase shift inserted into different positions. Then it was used in SSB modulation scheme as a filter. In the scheme, the lower sideband experiences higher attenuation due to the negative slope in reflectivity spectrum. Thus the conversion from dual-sideband(DSB) to single sideband with carrier(SSB+C) can be easily achieved by using only one phase-shifted superstructure fiber Bragg grating. Also, the optical carrier-to-sideband ratio(OCSR) can be optimized by using grating with different oblique angle. In this paper, the OCSR could be optimized from 33.02 dB to 1.31 dB and a 60 GHz millimeter-wave was detected after photodiode. What′s more, a min BER of 1.966e-44 with 30-km fiber length was implemented which means that only using one phase-shifted superstructure FBG can improve the link performance greatly.