A networked composite (Pd@PANI), which is self-assemblied freely from Pd (core) @polyaniline (shell) nanoparticles, has been prepared successfully by a facilely one-step approach. Owing to the conductive environment and acid-doped behavior provided by PANI, the composite exhibits highly catalytic ability in the reaction involving acidic reactants. For instance, in the HCOOH electro-oxidation, 9.16 times of specific activity (comparing with that when using commercial Pd/C catalyst) is observed. Meanwhile, the as prepared product is unable to catalyze some other systems like the electro-oxidation of C2H5OH, showing novel and unique selectivity. Those would open up new routes for synthesizing high-performance Pd-based catalysts, and could also shed some light on synthesizing new types of selective catalysts. (C) 2017 Published by Elsevier B.V.