Correlative microscopy approach by combining structural and chemical information on the same region of interest is a powerful but essential method to characterize the nanostructured phases statistically. κ phases of four different types with varied dimensions, morphology and composition form an inherent part of Nickel Aluminum Bronze (NAB) alloy. Such materials when produced by additive manufacturing methods such as wire-arc results in the formation of heterogeneous microstructure containing metastable phases of unique morphology. In order to understand the consistency of phase formation and microstructure evolution, two distinct layers L1 and L2 along the build direction were studied using novel, multiscale correlative microscopy approach utilizing techniques such as SEM-STEM, EDS, TKD, TEM and APT. The adopted correlative approach enabled in the visualization of different κ phases and quantifying them in terms of their size, number density, phase fraction etc. In comparison with the reported as-cast microstructure, the κ phases of wire-arc additive manufactured (WAAM) NAB exhibited an order of magnitude difference in sizes, significant variation in morphology and distribution. While the microstructural variation between the layers L1 and L2 were insignificant, the κ phases formed during WAAM and their local composition were in good agreement with CALPHAD (CALculation of PHAse Diagram) predictions at comparable cooling rates as that prevalent during WAAM. Therefore, the novel correlative microscopy approach employed in this work provided crucial insights into the microstructural heterogeneities, composition variation especially that of κ phases along the build direction of WAAM NAB suggesting that these methods are relevant for the understanding of additive manufactured materials.