Five functionalized porous coordination polymers 1–5 with highly ordered amide groups in the channels show notable interaction with guest molecules. The amide groups functioned as trigger sites and catalytically driven forces to activate substrate proximity within the pores. Catalytic studies on catalysts with different pore radii and substrates with different molecular sizes revealed that these porous materials are heterogeneous, efficient and reusable catalysts for the size-selective Knoevenagel condensation reaction. The solids were stable after the reactions and were easily recycled and reused under the reaction conditions. Most importantly, compound 3 with two different functionalities decorating the porous wall displays an elegant example of cooperative catalysis.