Macrostructured MCM-41 supports with bimodal pore size distribution were synthesized by a new and simpler dual-templating method. Skeleton structured MCM-41(Sk-MCM-41/PS) which consists of continuous network partially filling the interstices around polystyrene (PS) beads has high surface area, high mesopore volume and well defined macropore structure than other ones. Platinum catalysts supported on the macrostructured MCM-41 were studied for the selective catalytic reduction (SCR) under lean burn condition. Pt/Sk-MCM-41/PS catalyst not only showed better catalytic activity for NO reduction when using xylene and dodecane as reducing agent, but also improved the adsorption dynamics of those bulky hydrocarbons. Better accessibility of hydrocarbons must be provided due to the presence of macropores in Pt/Sk-MCM-41/PS.