It has been recently reported that engineering the pores within alloy nanoparticles leads to improvement in the electrochemical activity of nanoparticle catalysts due to the enhanced electrochemical active surface areas. However, to date, few works have reported the tailoring intraporosity within alloy nanoparticle networks. In this study, a different and innovative approach was adopted to yield a network-like PtCo catalyst composed of intraporous nanoparticles used a cotton-like PtCo precursor material. It was found that the network-like structure and intrapores within the nanoparticles could co-evolve after careful controlled electrochemical dealloying, whereby Pt-rich surface was formed during the leaching out of Co in the first 13th potentiostatic cyclic voltammetry cycles from +0.056 to +1.256 V vs. RHE. Electrochemical data also showed that the mass and area activity of the obtained PtCo networks toward methanol oxidation reaction (MOR) was nearly 3.9, 2.0 and 2.1 times higher than that of commercial Pt/C, PtRu/C catalyst respectively, and much higher than that of Pt3Co networks made of only solid nanoparticles. Moreover, it was observed that such networks exhibited high CO oxidation ability whilst maintaining high catalytic durability under an applied potential of + 0.756 V vs. RHE. It was found that developing network-like catalysts composed of porous nanoparticles can be an efficient strategy to improve the catalytic activity and durability of fuel cell catalysts. (C) 2017 Published by Elsevier Ltd.