A highly linear W-band receiver front-end based on higher-order optical sideband (OSB) processing is proposed and experimentally demonstrated. Two-tone analysis shows that by manipulating higher-order OSBs, the third-order intermodulation distortion (IMD3) introduced by optoelectronic components (mainly modulators) in the receiver front-end can be further suppressed, and a 9 dB improvement of the ratio of the fundamental and IMD3 can be attained. In the experiment, the spurious-free dynamic range of the W-band receiver front-end is up to 122.1 dB·Hz2/3, with improvement by 9 dB compared with that of only processing the five OSBs.