Light management and electrical isolation are essential for the majority of optoelectronic nanowire (NW) devices. Here, we present a cost-effective technique, based on vapor-phase deposition of parylene-C and subsequent annealing, that provides conformal encapsulation, anti-reflective coating, improved optical properties, and electrical insulation for GaAs nanowires. The process presented allows facile encapsulation and insulation that is suitable for any nanowire structure. In particular, the parylene-C encapsulation functions as an efficient antireflection coating for the nanowires, with reflectivity down to <1% in the visible spectrum. Furthermore, the parylene-C coating increases photoluminescence intensity, suggesting improved light guiding to the NWs. Finally, based on this process, a NW LED was fabricated, which showed good diode performance and a clear electroluminescence signal. We believe the process can expand the fabrication possibilities and improve the performance of optoelectronic nanowire devices.