A facile method for the synthesis of polyaniline-polypyrrole composite materials with network morphology is developed based on polyaniline nanofibers covered by a thin layer of polypyrrole via vapor phase polymerization. The hydrogen storage capacity of the composites is evaluated at room temperature exhibits a twofold increase in hydrogen storage capacity. The HCl-doped polyaniline nanofibers exhibit a storage capacity of 0.46 wt%, whereas the polyaniline-polypyrrole composites could store 0.91 wt% of hydrogen gas. In addition, the effect of the dopant type, counteranion size, and the doping with palladium nanoparticles on the storage properties are also investigated.