The present invention is process of synthesizing guaiacol, and relates to the application of catalyst in catalytically synthesizing guaiacol through the solid phase alkylation reaction between catechol and methanol. The catalyst has active component of ammonium metatungstate, sodium tungstate, ammonium molybdenum, ammonium biphosphate, ammonium phosphate, ammonium chromate or silicotungstic acid; and carrier of active carbon, SiO2, ZnO, Al2O3, TiO2, BaCO3 or CaO; and active component supporting amount of 2.1-30.2 wt%. The process of synthesizing guaiacol has catalytic reaction temperature of 533-573 K, the molar ratio between catechol and methanol of 1/7-1/2.5, and catalyst amount of 0.84-2.8 weight portions. During the process, the mixed solution of catechol and methanol is fed to the pre-heater in the flow rate of 0.3-2ml/hr, gasified and reacted catalytically at the temperature of 533-573 K.