Longan is a delicious subtropical fruit with great health-beneficial effects. It has been utilized for disease prevention and health care since ancient age. To explore the chemicals responsible for the health benefits, water-soluble polysaccharides were extracted from longan flesh in this work. A pure polysaccharide (LPS1) was obtained through column purification. Analysis by gas chromatography showed LPS1 was a homopolysaccharide of glucose with glycosidic linkage of →6)-d-Glc-(1→. Nuclear magnetic resonance (NMR) spectra indicated that the configuration of anomeric carbon in glucose residual was α-form. The polysaccharide structure was further confirmed to be (1→6)-α-d-glucan by chemcial shift of C6. The molecular weight of LPS1 was calculated to be 108 kDa, which had 661 glucose residuals. Anticancer assay showed that LPS1 had anticancer activity against the growth of HepG2 cells to a certain extent. However, it did not show any cytotoxicity against MCF-7 breast cancer cells.