A novel scheme for implementing high-performance optical single-sideband (OSSB) modulation based on a dual-drive Mach-Zehnder modulator (MZM) and a 120°hybrid coupler is proposed and demonstrated. A RF signal is divided by the 120°h ybrid coupler into two parts with equal powers and a phase difference of 120°, and then, led to the two RF ports of the dual-drive MZM. With a proper dc bias, an OSSB signal with the −1st and +2nd-order sidebands (or the +1st and −2nd-order sidebands) suppressed is generated. A numerical simulation and a proof-ofconcept experiment are carried out. As compared with the conventional OSSB modulation based on a 90°hybrid coupler, the suppression of the +2nd (or −2nd)-order sideband improves evidently the performance when the OSSB modulation is applied in a radio-over-fiber system or an optical vector network analyzer.Index Terms-Microwave photonics, optical single-sideband (OSSB) modulation, optical vector network analysis, radio-overfiber (RoF).