Hollow polymer capsules offer an approach for storage of hydrogen. Thus, in this paper, hollow poly(vinylidene fluoride) capsules were prepared by phase inversion of a polyvinylidene fluoride solution containing sodium borohydride that reacts with water to produce hydrogen during the phase separation. The effects of additives on the structure of the capsules were observed by scanning electronic microscopy and on the adsorption property were investigated by adsorbing sodium borohydride. The effects of the amount of capsules, concentration of sodium borohydride, and temperature on hydrogen production were studied via catalytic hydrolysis of sodium borohydride in aqueous solution. It was noticed that the capsules have good catalytic activity for hydrolysis of sodium borohydride with an activation energy of 49.3kJmol(-1). And the capsules can be used for adsorption of sodium borohydride in tetrahydrofuran before catalytic hydrolysis of sodium borohydride in water. Copyright (c) 2014 John Wiley & Sons, Ltd.