In this work, two new kinds of boronic acid functioned sorbents (HCLPH-N3@PCAPBA and HCLPH@N3-PBA) based on emulsion reactors coupled with click chemistry and boronate affinity were developed for the separation of naringin (NRG). The new clickable boronate ligands 3-(prop-2-ynyloxycarbonylamino) phenylboronic acid (PCAPBA) and azide phenylboronic acid (N3-PBA) were utilized as functional monomers for the specific separation and purification of NRG molecules, respectively. The pore structure of macroporous polymers were adjusted via the hypercrosslinking reactions, which can effectively increase their specific surface area and provide abundant recognition sites. The resulting HCLPH-N3@PCAPBA and HCLPH@N3-PBA exhibited fast equilibrium adsorption at 120 min, and their maximum absorption amounts were 29.85 μmol g−1 and 41.27 μmol g−1 at 303 K, respectively. The HCLPH-N3@PCAPBA and HCLPH@N3-PBA demonstrated remarkable stability in six cycles of adsorption–desorption experiments (88.48% and 92.02%, respectively). Furthermore, the HCLPH@N3-PBA achieved an efficient extraction 93.4% for the commercially available NRG. Our findings provided an idea for constructing hierarchically porous high-surface-area polymers with fast penetrability and various abundant binding sites have great potential for separation and purification of industrial samples.