Liver cancer is the third leading cause of cancer death, with high incidence and poor treatment effect. In recent years, polysaccharides have attracted more and more attention in the research field of anti-liver cancer because of their high efficiency, low toxicity, good biocompatibility, wide sources and low cost. Polysaccharides have been proven to have good anti-liver cancer activity. In this paper, the pathways and molecular mechanisms of polysaccharides against liver cancer were reviewed in detail. Polysaccharides exert anti-liver cancer activity by blocking cell cycle, inducing apoptosis, regulating immunity, inhibiting cancer cell metastasis, inhibiting tumor angiogenesis and so on. The primary structure and chain conformation of polysaccharides have an important influence on their anti-liver cancer activity. Structural modification enhanced the anti-liver cancer activity of polysaccharides. Polysaccharides have good attenuated and synergistic effects on chemotherapy drugs. Polysaccharides can be used as functional carriers to construct intelligent nano drug delivery systems (DDS) targeting liver cancer. This review can provide theoretical support for the further development and application of polysaccharides in the field of anti-liver cancer, and provide theoretical reference and clues for relevant researchers in food, nutrition, medicine and other fields.