Chlorella contains a variety of polysaccharides with complex composition and structure, which are composed of various monosaccharides such as galactose, rhamnose, glucose, arabinose, mannose, xylose and glucuronic acid. The glycosidic linkages of polysaccharides are diverse, including α-1,6-glucose, β-1,3-galactose, α-1,6-galactose, α-1,3-rhamnose, α-1,2-rhamnose, α-1,5-arabinose, α-1,6-mannose and β-1,4-xylose. Some polysaccharides are modified by methylation, sulfation and acetylation. Meanwhile, many studies have shown that polysaccharides have multiple functions such as immunoregulatory, anti-inflammatory, antioxidant, anti-tumor, antibacterial and intestinal flora-regulatory effects. At present, monosaccharide composition analysis, methylation combined with gas chromatography-mass spectrometry (GC-MS) and two-dimensional nuclear magnetic resonance (2D-NMR) spectroscopy are mainly used for research on the structure of chlorella polysaccharides such as analysis of monosaccharide composition, glycosidic bond types, branch chain substitution positions and branch chain types. This review hopes to provide valuable information for the fine structural analysis and structure-activity relationship study of polysaccharides from Chlorella.