Recently, the vectorial nonlinear optical processes driven by spin‐orbit coupling (SOC) light have come to the fore, leading to striking optical phenomena and important applications both in classical and quantum optics. However, research on the SOC‐mediated light‐atom interactions is still in its infancy. Here, the generation and manipulation of SOC mode through a vectorial four‐wave mixing (FWM) process in 85Rb vapor is demonstrated. Under the excitation of two SOC pump beams, multiple FWM paths can be simultaneously established due to the rich atomic Zeeman sublevels coupling with different circularly polarized components of SOC fields. A higher‐order cylindrical or more general SOC FWM signal is observed in the vectorial FWM process, which obeys angular momentum conservation and Gouy phase matching. In particular, quantum interference between different FWM paths plays a crucial role in manipulating the SOC mode of the generated FWM signal, revealing that the conversion of SOC mode is intrinsically quantum. This work provides a pathway toward deeper insight into the vectorial nonlinear optical processes and may advance technology for shaping spatially structured light, which is essential in applications such as nonlinear polarization imaging and the optical communication realm.