Poly(methyl acrylate)s bearing an amino adamantyl group were prepared via atom transfer radical polymerization (ATRP). The amino adamantyl (amantadine) group was incorporated into the polymer by homopolymerization as well as by copolymerization of acrylate bearing amantadine functional group. The rate of ATRP was slow compared to the rate of ATRP of methyl acrylate or adamantyl containing acrylate. It is due to the interaction of amine group of amantadine with Cu catalyst. H-1 NMR, matrix assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and gel permeation chromatography (GPC) analysis showed that the polymers had well-defined molecular weight and amino adamantyl functional group. Interestingly, this amine group was further reacted with epoxy group of the tailor-made poly(glycidyl methacrylate) (PGMA) to produce hydrogen-bonded polymers having porous network structure. It was evidenced by Field-emission scanning electron microscopy (FESEM) analysis, differential scanning calorimetry (DSC) analysis as well as by molecular modeling.