Abstract: To improve the nonlinear optical (NLO) properties of materials, the porphyrins were modified by post-functionalizations using typical 2+2 click reactions. Their NLO properties were studied by Z scan technology. The effect of the different conjugated-systems and electron-withdrawing properties on NLO properties of the novel porphyrins was discussed based on the different chemical structures (kinds of the central ions and the click moieties). One special NLO phenomena was observed here. As the side groups, the click moieties strongly affected the third-order NLO responses, and all the compounds exhibited the RSA-SA reversed NLO properties.