A polyaniline/graphene oxide composite was readily synthesized by liquidliquid interface polymerization of aniline in the presence of a sulfonated graphene oxide suspension using hydrogen peroxide and iron(III) chloride as oxidants. Subsequently, nickel nanoparticles were decorated on the synthesized hybrid material and used for the hydrogenation of phenylacetylene and its derivatives at room temperature under 100 psi of hydrogen pressure. The synthesized hybrid catalyst showed excellent catalytic activity and was readily recovered by centrifugation at the end of the reaction. The recovered catalyst was successfully used for several runs without any significant loss in the catalytic activity. Importantly, no leaching was observed during this course.