Novel solid acid-base catalysts with aluminum and nitrogen were prepared from phenolic compounds and formaldehyde by using triblock copolymer Pluronic F127 as a template via evaporation induced organic-organic assembly method. The catalysts were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectra (XPS). The acid-base properties of the catalyst were determined by temperature programmed desorption (TPD) using CO2 and NH3 as probe molecules. The side chain alkylation of toluene with methanol over the catalyst was studied, the results demonstrated that the catalyst Cat-TDMMP was of the higher activity [(ethylbenzene + styrene) yield was 41.0%] than the conventional alkali exchanged zeolites [(ethylbenzene + styrene) yield was about 20%]. This fact may due to the strength and distance of the specific surface acid-base pairs of the catalyst, which are favored to bimolecular side-chain alkylation reaction.