With broader available bandwidth, W-band wireless transmission has attracted a lot of interests for future Giga-bit communication. In this article, we experimentally demonstrate W-band radio-over-fiber (RoF) system employing single-sideband single-carrier (SSB-SC) modulation with lower peak-to-average-power ratio (PAPR) than orthogonal frequency division multiplex (OFDM). To overcome the inter-symbol interference (ISI) of the penalty from uneven frequency response and SSB-SC modulation, frequency domain equalizer (FDE) and decision feedback equalizer (DFE) are implemented. We discuss the maximum available bandwidth of different modulation formats between SSB-SC and OFDM signals at the BER below forward error correction (FEC) threshold (3.8 × 10-3). Up to 50-Gbps 32-QAM SSB-SC signals with spectral efficiency of 5 bit/s/Hz can be achieved.