Abstract: Organic dyes, as primary pollutants in printing and dyeing wastewater, are characterized by their recalcitrance to degradation and widespread ecotoxicity, posing significant threats to aquatic ecosystems and human health. However, conventional wastewater treatment methods often fail to achieve efficient, selective recovery and resource-oriented utilization of individual dye molecules. Based on this, surface molecularly imprinted polymers (ARS/SMIPs) targeting a representative anthraquinone dye (Alizarin Red S, ARS) was developed by strategically incorporating multiple intermolecular interactions, including π–π stacking, electrostatic attraction, and hydrogen bonding. The structural and morphological properties of the synthesized ARS/SMIPs were systematically characterized using FT-IR, SEM, XRD, VSM and TG. Results demonstrate that ARS/SMIPs exhibit a uniformly sized, roughly spherical morphology with favorable dispersibility and show efficient adsorption capacity (419.23 mg·g⁻¹) towards alizarin, rapid enrichment (within 5 s) and prominent regeneration performance (maintaining an adsorption capacity of approximately 300 mg·g⁻¹ even after the 10^th cycles). Importantly, in a senary competitive adsorption environment, the adsorption efficiency of ARS/SMIPs for interferents is as low as 12.53% for 100% of ARS. Furthermore, the spiked recovery of ARS in real printing and dyeing wastewater reached 96.23% with negligible adsorption towards impurities. This work provides a promising strategy for selective separation and resource recovery of specific dyes from wastewater, holding great potential for practical industrial applications.