Exploitation of low‐dimensional metal‐oxide semiconductor nanowires (MOS NWs) with peculiar and radial coaxial architectures is of great significance for constructing nanoscale, high‐performance, multi‐module integrable functional electronic products. Here, highly ordered In2O3@ZnO coaxial NW arrays (CNWA) using a simple and economical electrospinning technique are synthesized and assembled into field‐effect transistors (FETs). Featuring strong carrier effusion efficiency at the In2O3@ZnO circular heterogeneous interface, the field effect mobility (εFE) gets an intrinsic improvement and can reach as high as 202.3 cm2 V‒1 s‒1 for high‐k‐based CNWA FETs, which exceeds the performance of oxide‐based FETs devices reported by far. Furthermore, the unique structural advantages endowing In2O3@ZnO CNWA FETs with excellent optoelectronic coupling capabilities are identified, for which further optoelectronic detection and artificial photonic synaptic devices are constructed and functional simulations are implemented. This work offers new insights in designing optoelectronics and artificial synapses to process and recognize information for neuromorphic computing and artificial intelligence applications.