A simple and effective hydrothermal synthesis of spherical α-Ni(OH)2 particles and α-Ni(OH)2/carbon composites was proposed. The mechanism of ultrafine α-Ni(OH)2 phase forming and correlations between synthesis conditions, morphology, electrical conductivity were analyzed. It was found that carbon nanoparticles form an electric conductive cover on nickel hydroxide microparticles during synthesis which increases overall electronic conductivity of the composite material. α-Ni(OH)2 and α-Ni(OH)2/C samples were tested as electrodes for hybrid supercapacitors. It was found that carbon coverings stabilize α-Ni(OH)2 phase in the alkaline medium. The comparison of the influence of laser irradiation and ultrasonic treatment on the electrochemical performance of the obtained materials was made.