Cross-linked poly acidic ionic liquids (MPM-C6V-SO3CF3-IL) with mesoporous and macroporous network structure have been synthesized in different solvents. The novel solid acid catalyst with special network structure has a large surface area (103.83 m(2)/g), large pore volume (0.72 cm(3)/g) and abundant mesopores and macro pores, which help to improve the contact between active site and reactants. Catalytic performance of catalyst was investigated through alkylation of o-xylene and styrene. Different reaction parameters specifically solvent on obtained catalyst and production of PXE were systematically investigated. Under optimal reaction conditions (reaction time was 3 h, reaction temperature was 120 degrees C, catalyst amount was 0.17 g (0.5 wt%), and o-xylene/styrene mass ratio was 7.5:1), a high conversion of styrene (100%) and 1,2-diphenylethane (PXE) yield of 99.67% was obtained, which is superior to commercial acid in liquid and even previous acids synthesized by our own group. Moreover, catalyst could keep relatively high thermostability under reaction and are easy to be separated and recycled from the solution, which are critical for heterogeneous solid catalysts. Thus, this novel catalyst can be potentially applied in other acidic reactions.