Two types of polymer nanocomposite particles were developed through electroless plating of nickel onto polymer nanospheres for hydrogen production from sodium borohydride solution. Different distributions of Ni in the polymer particles can be obtained either in polymer core-metal shell morphology or homogeneously hybridized morphology, depending on the hydrophilicity of the polymers. The Ni–polymer particles exhibited high catalytic activities in hydrogen production reactions with excellent recyclability, which is important in portable clean energy generation technology.