A one-pot wet-chemical co-reduction route is designed for preparation of porous dandelion-like Au@Pd core-shell nanostructures in-situ grown on reduced grapheneoxide (Au@Pd/rGO) without using any premade seed. Cetyltrimethylammonium chloride (CTAC) and iodide ion (I) play important roles in this synthetic procedure. Particularly, the Pd shell thickness, particle size, composition and catalytic activity can be tuned by adjusting the concentrations of I. The effects of composition and structure of the as-synthesized nanocomposites on the catalytic performance are investigated. The dandelion-like Au@Pd/rGO exhibited higher catalytic activity and stronger tolerance to carbonaceous species poisoning for methanol oxidation reaction (MOR) in contrast with Pd/rGO and commercial Pd/C catalysts in alkaline media. This strategy offers a new approach for controlled synthesis of novel nanocatalysts with enhanced catalytic performances in fuel cell. (C) 2016 Elsevier Ltd. All rights reserved.