We herein firstly presented supramolecularly imprinted polymeric (SMIP) solid phase microextraction (SPME) coatings which showed synergetic recognition for nitrophenols and bisphenol A. A series of beta-cyclodextrins (beta-CD) with different substituents were successfully designed and synthesized. It was employed as supramolecular functional monomers for SMIPs. The orderly assembling structures settled down under the molecular imprinting process. The four of SMIPs solid phase microextraction coatings showed good selectivity for the template and could be used to extract 4-NP in real water samples. Furthermore, the inclusion effects of derived beta-CDs with the 4-NP were investigated by measuring the UV vis spectra and the theoretical calculations. The strongest intermolecular force is come from the supramolecular complex of 4-NP and beta-CD-4 which shows the strongest UV-vis spectra absorption value. Meanwhile, the difference of the theoretical calculations value coming from the system of derived beta-CDs and 4-NP is the largest, revealing the strongest electronic interactions between derived beta-CD-4 and 4-NP. Therefore, these polymers possess inclusion interactions from P-cyclodextrin cavities and hydrogen bonding interactions from molecular imprinting. Multiple adsorptions triggered off a synergetic recognition for target analytes. The SMIPs also performed highly selective recognition in complex real water sample with sensitive detection limits.