Alkenylations of p-xylene with phenylacetylene over various zeolites like HY, H-Beta, and H-ZSM-5 have been performed. Effects of the types of zeolite and pretreatment conditions, such as ion exchange times, calcination temperature, and HCl concentration for dealumination, on the catalytic properties have been studied. Moreover, the HY, H-Beta, and MCM-41 supported both H3PW12O40 and H3SiW12O40 solid acid catalysts, which were employed to promote the alkenylation reaction. It has been found that H3PW12O40/MCM-41 mesoporous solid acid could become a promising catalyst for alkenylation of p-xylene. The possible mechanism of alkenylation of p-xylene with phenylacetylene over solid acid catalysts is also proposed.