Integration of quadrature-amplitude-modulation (QAM) modulation and millimeter-wave (mm-wave) technology ensures a concise enhancement of transmission capacity and peak data rates in radio-over-fiber (RoF) systems. Nevertheless, with the continuous development of new-generation mobile applications, higher demands on access flexibility have also been formulated. We propose a novel, to the best of our knowledge, dual 16-QAM-modulated mm-wave signal generation scheme for the simultaneous generation and transmission of two independent 16-QAM signals with different carrier frequencies, enhancing the channel capacity, spectrum efficiency, and access flexibility of the RoF systems. In our proposed scheme, the generation of the optical dual 16-QAM-modulated mm-wave signals is implemented by a precoding-based optical in-phase/quadrature (I/Q) modulator operating at optical carrier suppression (OCS) mode, and their detection is implemented by a single photodetector (PD). At the transmitter side, two independent driving QAM vector radio-frequency (RF) signals with precoding, generated via digital signal process (DSP), are fed into two parallel Mach–Zehnder modulators (MZMs) of an I/Q modulator to implement OCS modulation. The I/Q modulator generates optical carriers carrying both information from different QAM signals simultaneously. After square-law detection in a single PD, we generate the desired dual 16-QAM-modulated mm-wave signals with photonic frequency-doubling and recover the original 16-QAM signals without information distortion. Based on our proposed scheme, we experimentally demonstrate the simultaneous generation and transmission of 2-Gbaud dual 16-QAM-modulated mm-wave signals with carrier frequencies of 26 GHz and 40 GHz, respectively. After transmission over 10-km single-mode fiber (SMF) link and 1.2-m wireless link, the dual 16-QAM signals can be successfully separated and demodulated by a common DSP. Bit-error ratios (BERs) of both recovered 16-QAM signals can reach the hard-decision forward-error-correction (HD-FEC) threshold of 3.8×10−3. Compared with the existing schemes, our scheme only requires one-half of the driving frequency to generate dual 16-QAM-modulated mm-wave signals with the same carrier frequency. The result indicates that our proposed scheme can lower bandwidth requirements for optoelectronics devices, along with implementing better spectral efficiency and receiver sensitivity, which is more applicable to the demands for increased system capacity and multi-frequency access flexibility in future systems.