We present a W-band fiber-wireless transmission system based on a nonlinear frequency multiplier for high-speed wireless short range access applications. By implementing a baseband digital signal predistortion scheme, intensive nonlinear distortions induced in a sextuple frequency multiplier can be effectively pre-compensated. Without using costly W-band components, a transmission system with 26km fiber and 4m wireless transmission operating at 99.6GHz is experimentally validated. Adjacent-channel power ratio (ACPR) improvements for IQ-modulated vector signals are guaranteed and transmission performances for fiber and wireless channels are studied. This W-band predistortion technique is a promising candidate for applications in high capacity wireless-fiber access systems.