Recent developments in fabrication techniques and extensive investigations of the physical properties of III-V semiconductor nanowires (NWs), such as GaAs NWs, have demonstrated their potential for a multitude of advanced electronic and photonics applications. Alloying of GaAs with nitrogen can further enhance the performance and extend the device functionality via intentional defects and heterostructure engineering in GaNAs and GaAs/GaNAs coaxial NWs. In this work, it is shown that incorporation of nitrogen in GaAs NWs leads to formation of three-dimensional confining potentials caused by short-range fluctuations in the nitrogen composition, which are superimposed on long-range alloy disorder. The resulting localized states exhibit a quantum-dot like electronic structure, forming optically active states in the GaNAs shell. By directly correlating the structural and optical properties of individual NWs, it is also shown that formation of the localized states is efficient in pure zinc-blende wires and is further facilitated by structural polymorphism. The light emission from these localized states is found to be spectrally narrow (∼50-130 μeV) and is highly polarized (up to 100%) with the preferable polarization direction orthogonal to the NW axis, suggesting a preferential orientation of the localization potential. These properties of self-assembled nano-emitters embedded in the GaNAs-based nanowire structures may be attractive for potential optoelectronic applications.