In this study, we discuss the influence of SiH flow rates on the structural and optical properties of GaN nanowires (NWs) with multiple-quantum-shells (MQSs). To this end, we prepared two n-GaN core NW samples with different SiH flow rates. Subsequently, MQS active layers of the same structure were grown on each n-GaN core NW under identical growth conditions. The samples were characterized by scanning electron microscopy, scanning transmission electron microscopy, energy-dispersive X-ray, and cathodoluminescence (CL) mapping. From the experimental results, we ascertained that a Si-rich layer was created between the sidewall of the NWs and MQSs, in which the number of Si atoms was mainly determined by the SiH flow rate. These Si atoms diffused into the MQSs during the growth, and significantly impacted the structural and optical properties, such as the shape and crystalline quality of the MQSs and NWs, and the CL intensity of the MQSs. On the basis of experimental results, we conclude that the SiH flow rate during the NW growth plays a critical role in the performance of an MQS-based optoelectronic semiconductor device. 4 4 4 4