A new material called as porous aromatic frameworks modified graphene oxide (PAFs-GO) was synthesized, and it was used as an adsorbent in pipette-tip SPE for the effective purification and enrichment of theophylline in tea sample by HPLC. The properties of PAFs-GO were characterized by field emission SEM, FTIR, thermogravimetry analysis and Brunauer Emmett Teller N-2 adsorption-desorption analysis. The results of static adsorption and dynamic adsorption test showed PAFs-GO had higher adsorption ability (93.25 mg/g) than graphene oxide. The LOD and LOQ of the method were 0.0141 and 0.0471 mu g/mL, respectively. The acceptable method reproducibility was found as intra- and inter-day precisions, yielding the RSDs <4.62%. By introducing PAFs as support skeleton, the specific surface area of GO was effectively increased, and the penetrability was improved. Studies showed that the proposed method had been successfully applied for purification and enrichment of theophylline in complex tea matrix.