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In this study, an enzyme‐assisted extraction method was used to extract Orchis chusua D. Don (Salep) polysaccharide (SP), which was then modified by sulfation, acetylation, phosphorylation, and carboxymethylation to obtain modified polysaccharides. Furthermore, their degree of substitution, chemical composition, and molecular weight were evaluated. The primary structural features were characterized by UV spectra, FT‐IR spectra, Congo‐red test, and scanning electron microscope. The phosphorylated polysaccharide (SP‐P) was demonstrated the highest scavenging ability on hydroxyl radical and growth‐promoting activity on Lactobacillus Bulgaricus. The carboxymethylated polysaccharide (SP‐C) was exhibited the strongest DPPH and ABTS radical scavenging effects. The acetylated polysaccharide (SP‐A) displayed the best proliferation effects on Bifidobacterium adolescentis, whereas the sulfated polysaccharide (SP‐S) maintained moderately stable antioxidant and probiotic ability. These findings indicate that the modified polysaccharides had their potential significance as new antioxidants and probiotics for the food industry. Practical Application This article provides a new source for the development of polysaccharide derivatives as new antioxidants and probiotics for the food industry.

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