Efficient removal of uranyl ions from wastewater requires excellent selectivity of the adsorbents. Herein, we report a new strategy using a high monomer/template molar ratio of 500:1 to prepare surface ion-imprinted brewer's spent grain (IIP-BSG) for selective U(VI) removal using binary functional monomers (2-hydroxyethyl methacrylate and diethyl vinylphosphonate) with high site accessibility and easy template removal. IIP-BSG exhibits a maximum U(VI) adsorption capacity of 165.7 mg/g, a high selectivity toward U(VI) in the presence of an excess amount of Eu(III) (Eu/U molar ratio = 20), a good tolerance of salinity, and a high reusability. In addition, mechanism studies have revealed electrostatic interaction and a coordination of uranyl ions by carboxyl and phosphoryl groups, the predominant contribution of high-energy (specific) sites during selective adsorption, and internal mass transfer as the rate-controlling step of U(VI) adsorption. Furthermore, IIP-BSG shows great potentials to separate U(VI) from lanthanides in simulated nuclear wastewater (pH ₀ = 3.5) and selectively concentrate U(VI) from simulated mine water (pH ₀ = 7.1). This study proves that the ion-imprinting effect can be achieved using a very low template amount with reduced production cost and secondary pollution, which benefits large-scale promotion of the ion-imprinted materials for selective uranyl ions removal.