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A heterogeneous catalyst (HPW/mpg‐C3N4) for the alkylation of o‐xylene and styrene reaction was acquired by the immobilization of phosphotungstic acid (HPW) on mesoporous graphitic carbon nitride (mpg‐C3N4) through electrostatic interaction. The results of Fourier transform infrared spectroscopy (FT‐IR), X‐ray powder diffraction (XRD), X‐ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA) proved that HPW was successfully immobilized on the protonated mpg‐C3N4 by electrostatic interaction. The textural properties and morphology of HPW/mpg‐C3N4 were characterized by N2 adsorption–desorption, scanning electron microscopy (SEM). Among them, 40% HPW/mpg‐C3N4 displays the best catalytic performance in the alkylation reaction with 91.8% yield and 96.5% selectivity to 1, 2‐diphenylethylane. Moreover, protonated mpg‐C3N4 not only displays as a support to facilitate great dispersion of HPW but also promotes the alkylation product diffusion effectively. Besides, the HPW/mpg‐C3N4 catalyst could be recycled easily without significant loss of catalytic activity, which is demonstrate by the recyclability of HPW/mpg‐C3N4 catalyst test. [ABSTRACT FROM AUTHOR]