During the last few years, there has been renewed interest in the monolithic integration of gold-free, Ternary III–As Antimonide (III–As–Sb) compound semiconductor materials on complementary metal-oxide-semiconductor (CMOS)—compatible silicon substrate to exploit its scalability, and relative abundance in high-performance and cost-effective integrated circuits based on the well-established technology. Ternary III–As–Sb nanowires (NWs) hold enormous promise for the fabrication of high-performance optoelectronic nanodevices with tunable bandgap. However, the direct epitaxial growth of gold-free ternary III–As–Sb NWs on silicon is extremely challenging, due to the surfactant effect of Sb. This review highlights the recent progress towards the monolithic integration of III–As–Sb NWs on Si. First, a comprehensive and in-depth review of recent progress made in the gold-free growth of III–As–Sb NWs directly on Si is explicated, followed by a detailed description of the root cause of Sb surfactant effect and its influence on the morphology and structural properties of Au-free ternary III–As–Sb NWs. Then, the various strategies that have been successfully deployed for mitigating the Sb surfactant effect for enhanced Sb incorporation are highlighted. Finally, recent advances made in the development of CMOS compatible, Ternary III–As–Sb NWs based, high-performance optoelectronic devices are elucidated.