D-band (110–170 GHz) is a promising direction for the future of 6th generation mobile networks (6G) for high-speed mobile communication since it has a large available bandwidth, and it can provide a peak rate of hundreds of Gbit/s. Compared with the traditional electrical approach, photonics millimeter wave (mm-wave) generation in D-band is more practical and effectively overcomes the bottleneck of electrical devices. However, long-distance D-band wireless transmission is still limited by some key factors such as large absorption loss and nonlinear noises. Deep neural network algorithms are regarded as an important technique to model the nonlinear wireless behavior, among which the study on complex-value equalization is critical, especially in coherent detection systems. Moreover, probabilistic shaping is useful to improve the transmission capacity but also causes an imbalanced machine learning issue. In this paper, we propose a novel complex-valued neural network equalizer coupled with balanced random oversampling (ROS). Thanks to the adaptive deep learning method for probabilistic shaping-quadrature amplitude modulation (PS-QAM), we successfully realize a 135 GHz 4Gbaud PS-16QAM with a shaping entropy of 3.56 bit/symbol wireless transmission over 4.6 km. The bit error ratio (BER) of 4Gbaud PS-16QAM can be decreased to a soft-decision forward error correction (SD-FEC) with a 25% overhead of 2×10−2. Therefore, we can achieve a net rate of an 11.4 Gbit/s D-band radio-over-fiber (ROF) delivery over 4.6 km air free wireless distance.