Nanostructured nickel hydroxide thin films are synthesized via a simple chemical bath deposition (CBD) method using nickel nitrate Ni(NO3)2 as the starting material. The deposition process is based on the thermal decomposition of ammonia-complexed nickel ions at 333K. The structural, surface morphological, optical, electrical and electrochemical properties of the films are examined. The nanocrystalline “β” phase of Ni(OH)2 is confirmed by the X-ray diffraction analysis. Scanning electron microscopy reveals a macroporous and interconnected honeycomb-like morphology. Optical absorption studies show that “β-Ni(OH)2” has a wide optical band-gap of 3.95eV. The negative temperature coefficient of the electrical resistance of “β-Ni(OH)2”, is attributed to the semiconducting nature of the material. The electrochemical properties of “β-Ni(OH)2” in KOH electrolyte are examined by cyclic voltammetric (CV) measurements. The scan-rate dependent voltammograms demonstrate pseudocapacitive behaviour when “β-Ni(OH)2” is employed as a working electrode in a three-electrode electrochemical cell containing 2M KOH electrolyte with a platinum counter electrode and a saturated calomel reference electrodes. A specific capacitance of ∼398×103 Fkg−1 is obtained.