Ni nanoarrays were synthesized by electroless-plating and shaped by an anodic aluminum oxide template. The as-plated arrays exhibited superparamagnetic (SM) ordering resulting from nanocrystalline microstructure. Ferromagnetic (FM) ordering was found to be restored as the arrays' crystallinity was enhanced upon post-annealing. The microstructure (crystallinity) and the FM ordering are strongly coupled, revealing a magneto-structural correlation for the arrays. The magnetostructural properties of the arrays can be controlled by post-annealing, where the magnetization is proportional to the annealing temperature. The electroless-plated arrays synthesized in this work display magnetic anisotropy not found in electroplated ones. This is likely attributed to the nature of the clusterlike microstructure, whose cluster-boundaries may confine the FM rotation within the cluster. The spin-polarization was probed by x-ray magnetic circular dichroism while the arrays underwent the SM→FM phase transition. The sum-rules results reveal that the total magnetization of the arrays is dominated by spin moment (mspin). The change in mspin is responsible for the SM→FM phase transition upon annealing, as well as for the loss of magnetization upon temperature increase that we observed macroscopically.