The present work utilizes Raman and infrared (IR) spectroscopy, supported by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) to re-examine the fine structural details of Ni(OH)2, which is a key material in many energy-related applications. This work also unifies the large body of literature on the topic. Samples were prepared by the galvanostatic basification of nickel salts and by aging the deposits in hot KOH solutions. A simplified model is presented consisting of two fundamental phases (α and β) of Ni(OH)2 and a range of possible structural disorder arising from factors such as impurities, hydration, and crystal defects. For the first time, all of the lattice modes of β-Ni(OH)2 have been identified and assigned using factor group analysis. Ni(OH)2 films can be rapidly identified in pure and mixed samples using Raman or IR spectroscopy by measuring their strong O–H stretching modes, which act as fingerprints. Thus, this work establishes methods to measure the phase, or phases, and disorder at a Ni(OH)2 sample surface and to correlate desired chemical properties to their structural origins. ; peer reviewed: yes ; NRC Pub: yes