As a by-product of the sugar industry containing many sugars, proteins, nitrogenous materials, and heavy metals, molasses is rarely used for polysaccharide production. In the present work, a Chaetomium globosum CGMCC 6882 polysaccharide was produced from sugarcane molasses (CGP-SM) was successfully produced from sugarcane molasses. The yield of CGP-SM was 5.83 ± 0.09 g/l and its protein content was 2.41 ± 0.12% (w/w). Structural analysis showed that CGP-SM was a crystalline and amorphous polysaccharide containing rhamnose, glucosamine, galactose, glucose, mannose, fructose, and glucuronic acid in the molar ratio of 10.31: 1.14: 2.07: 59.55: 42.65: 1.92: 9.63. Meanwhile, weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity (Mw/Mn) of CGP-SM were 28.37 KDa, 23.66 KDa, and 1.199, respectively. Furthermore, the bacteriostatic assay indicated that CGP-SM inhibited the growth of Escherichia coli and Staphylococcus aureus in a concentration-dependent manner, and its inhibitory effect on S. aureus was higher than that of E. coli. Above all, this work provides a green method for the production of bioactive polysaccharide from sugarcane molasses.