The daylily ( Baroni) flower is a traditional raw food material that is rich in a variety of nutrients. In particular, the content of polysaccharides in daylily is abundant and has been widely used as a functional component in food, cosmetics, medicine, and other industries. However, studies on the structure-effective relationship of daylily flower polysaccharides are still lacking. In view of this, daylily flower polysaccharides were isolated and purified, and their physical and chemical properties, structure, antioxidant activity, and adhesion-promoting effect on probiotics were evaluated. The results showed that a novel water-soluble polysaccharide (DPW) with an average molecular weight () of 2.224 kDa could be successfully isolated using column chromatography. Monosaccharide composition analysis showed that DPW only comprised glucose and fructose, with a molar ratio of 0.242:0.758. Through methylation and nuclear magnetic resonance (NMR) analysis, it was inferred that DPW belonged to the fructans group with a structure of α-D-Glcp-1→2-β-D-Fruf-1→(2-β-D-Fruf-1)→. Antioxidant analysis showed that DPW showed strong 2-Phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-Oxide (PTIO-scavenging activity with IC of 1.54 mg/mL. DPW of 1.25 to 5 mg/mL could significantly increase the adhesion rate of , , , and on Caco-2 cells. Considering the above results, the present study provides a theoretical basis and practical support for the development and application of daylily polysaccharides as a functional active ingredient.