FeCl3·6H2O was anchored in the pores of a layered crystalline imine-based mesoporous covalent organic framework (TPB-DMTP-COF) with surface area of 1200 m2/g and pores of 34 A, affording the material FeCl3@TPB-DMTP-COF that worked as iron based heterogeneous catalyst. This new porous material was used in the decarboxylative oxidation cross-coupling reaction of cinnamic acids showing good to excellent catalytic activity with good chemical yields and short reaction time. FeCl3@TPB-DMTP-COF exhibit moderate surface area (235 m2/g) and high thermal and chemical stability allowing it use for several catalytic cycles.