Abstract: Calixarene-based porous organic framework (CalixPOF) has been successfully synthesized by in situ solvent-assisted Friedel-Crafts coupling with 1, 2-dichloroethane as solvent and coupling agent.The chemical component and molecular structure of CalixPOF were characterized by Fourier Transform Infrared Spectra (FT-IR) and solid-state Nuclear Magnetic Resonance spectroscopy (¹³C-NMR), which verified the reaction mechanism.The specific surface area, microstructure, thermal stability and dye adsorption efficiency of CalixPOF were investigated by nitrogen adsorption, Scanning Electron Microscopy (SEM), Thermogravimetry (TG) and Ultraviolet-visible spectrum (UV-vis).Results show that CalixPOF with good thermal stability and high specific surface area, selective adsorption to methylene blue dye, can be obtained in situ solvent-assisted Friedel-Crafts coupling.A new method for the synthesis of novel porous polymer networks with host-guest microcavities was provided.