In the present work, novel molecularly imprinted polymer porous beads for the selective separation of copper ions have been synthesized by combining two material‐structuring techniques, namely, molecular imprinting and oil‐in‐water‐in‐oil emulsion polymerization. This method produces monodisperse spherical beads with an average diameter of ∼2–3 mm, in contrast to adsorbents produced in the traditional way of grinding and sieving. Field‐emission scanning electron microscopy indicates that the beads are porous in nature with interconnected pores of about 25–50 μm. Brunner–Emmett–Teller analysis shows that the ion‐imprinted beads possess a high surface area (8.05 m2/g), and the total pore volume is determined to be 0.00823 cm3/g. As a result of the highly porous nature and ion‐imprinting, the beads exhibit a superior adsorption capacity (84 mg/g) towards copper than the non‐imprinted material (22 mg/g). Furthermore, selectivity studies indicate that imprinted beads show splendid recognizing ability, that is, nearly fourfold greater selective binding for Cu2+ in comparison to the other bivalent ions such as Mn2+, Ni2+, Co2+, and Ca2+. The imprinted composite beads prepared in this study possess uniform porous morphology and may open up new possibilities for the selective removal of copper ions from waste water/contaminated matrices.