We experimentally built a photonics-aided long-distance large-capacity millimeter-wave wireless transmission system and demonstrated a delivery of 40 Gbit/s W-band 16-ary quadrature amplitude modulation (QAM) signal over 4600 m wireless distance at 88.5 GHz. Advanced offline digital signal processing algorithms are proposed and employed for signal recovery, which makes the bit-error ratio under 2.4×10-2. To the best of our knowledge, this is the first field-trial demonstration of >4km W-band 16QAM signal transmission, and the result achieves a record-breaking product of wireless transmission capacity and distance, i.e., 184 (Gbit/s)·km, for high-speed and long-distance W-band wireless communication.