ABSTRACT The leaves of Hemerocallis citrina Baroni ( H. citrina Baroni) are a promising source of bioactive polysaccharides (HCLP). However, the presence of abundant pigments in crude HCLP complicates subsequent purification and analysis, making an effective decolorization step essential. A model of decolorization conditions of HCLP was established using single factor and response surface methodology (RSM), and the optimal decolorization conditions were obtained. Subsequently, the HCLP‐0.1 was successfully isolated via DEAE‐52 cellulose column. Structural characterization revealed that HCLP‐0.1 has a molecular weight ( M w ) of 8317.64 Da, composed of Man, GlcN, Rha, GlcA, GalA, Glc, Gal, Xyl, and Ara. Furthermore, HCLP‐0.1 was characterized by α‐ and β‐pyranose configurations, crystallinity, and an irregular triple‐helical structure. Thermal analysis demonstrated excellent thermal stability. Antioxidant assays revealed that HCLP‐0.1 possesses significant concentration‐dependent (0.1–2.0 mg/mL) scavenging capacity against ABTS, hydroxyl, and DPPH radicals. These results support the potential of HCLP as a natural antioxidant, providing a solid basis for its future application in functional foods or pharmaceuticals.