A high-capacity spectral-efficient dual-polarization quadrature phase-shift keying (DP-QPSK)-polarization shift-keying (PolSK) hybrid modulation scheme for terrestrial free-space optics (FSO) transmission link is proposed and investigated. A DP-QPSK signal modulated at 300 Gbps and a PolSK signal modulated at 40 Gbps are simultaneously transmitted using a single optical carrier over the FSO link. The proposed link performance is investigated under different weather conditions, where the bit error rate metric is used to evaluate the performance of the PolSK modulated signal and the error vector magnitude parameter is used for the DP-QPSK signal. The FSO link range and the required received power are carefully explored. The conducted numerical simulations of the proposed system showed reliable 340-Gbps data transmission over link ranges varying from 1.6125 to 50 km depending on the weather conditions. The impact of the channel scintillation due to atmospheric turbulence is also investigated. The proposed high-speed FSO transmission system offers a promising solution for high-bandwidth hungry systems used for the internet of things, 5G, and smart cities. It can also be used in developing fronthaul/backhaul links for future wireless networks and optical access networks. The performance of the proposed transmission system is compared with recently published work in the literature.