Recently, the investigation of novel molecularly imprinted polymers(MIPs) has attracted a lot of interest and becomes a fascinating field. The phenobarbital(PHN) was taken as an imprinted molecule and the 2-vinyl-4,6-diamino-1,3,5-triazine(VDAT) was considered as a functional monomer in this study. The geometry optimization, natural bond orbital(NBO) charge, and molecular electrostatic potential(MEP) of PHN and VDAT were studied at the M062 X level belonging to one of the hybrid density functional theories. Furthermore, we discussed the bonding conditions of PHN molecular imprinted polymers(PHN-MIPs) via the hydrogen bond length and atoms in molecules(AIM) theory. The rebinding property of PHN-MIPs was also researched. The results of MEP and NBO charge analysis were coincident. The stability property was excellent when the ratio of PHN and VDAT was 1:4. Except the classic hydrogen bonds, non-classical hydrogen bonds also existed in the imprinted polymers. By simulating the rebinding energies between the pentobarbital(PNT), barbital(BAR), and PHN-MIPs after the elution of PHN, the rebinding property of PHN-MIPs to PHN was excellent when PNT and BAR existed all at once. This research can provide theoretical reference for the synthesis and characterization of novel PHN-MIPs. Recently, the investigation of novel molecularly imprinted polymers (MIPs) has attracted a lot of interest and becomes a fascinating field. The phenobarbital (PHN) was taken as an imprinted molecule and the 2-vinyl-4,6-diamino- The geometry optimization, natural bond orbital (NBO) charge, and molecular electrostatic potential (MEP) of PHN and VDAT were studied at the M062 X level belonging to one of the hybrid density functional theories. Furthermore, we discussed the bonding conditions of PHN molecular imprinted polymers (PHN-MIPs) via the hydrogen bond length and atoms in molecules (AIM) theory. The rebinding property of PHN-MIPs was also researched. results of MEP and NBO charge analysis were coincident. The stability property was excellent when the ratio of PHN and VDAT was 1: 4. Except the classic hydrogen bonds, non-classical hydrogen bonds also existed in the imprinted polymers. By simulating the rebinding en ergies between the pentobarbital (PNT), barbital (BAR), and PHN-MIPs after the elution of PHN, the rebinding property of PHN-MIPs to PHN was excellent when PNT and BAR existed all at once. This research can provide theoretical reference for the synthesis and characterization of novel PHN-MIPs.