A silver-based coordination polymer, [Ag₄(dpe)₄]·(butca)·13H₂O (CP 1), as an efficient adsorbent, has been successfully prepared by slow evaporation and used to conduct an adsorptive uptake of four typical organic dyes, including anionic methyl orange (MO), anionic congo red (CR), cationic methylene blue (MB) and cationic rhodamine B (RhB). The results demonstrated that CP 1 could remove anionic dyes from the aqueous solution more efficiently than cationic dyes, in which the maximum adsorption capacity of CP 1 towards MO and CR was 779 mg g⁻¹ and 739 mg g⁻¹, respectively. Based on the selective adsorption, CP 1 could quickly and efficiently separate the MO from the mixture of MO/MB via a self-made SPE column.