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A simple and green synthetic route based on the use of soluble starch as the template has been utilized to prepare novel Ni(OH)2/starch precursors. Nanoporous nickel oxide (NiO) and nickel nanoparticles/amorphous carbon (Ni/C) composites have been successfully prepared by thermal decomposition of the novel Ni(OH)2/starch precursors in air and in nitrogen, respectively. N2 adsorption–desorption measurements show the two final products having nanoporous structures. The electrochemical measurements indicate that the nanoporous NiO sample has a favorable faradaic pseudocapacitance behavior.