Several complexes with different mass ratios of hyaluronic acid to pectin were studied using AFM and IR at the room temperature kept by air conditioning. The results showed that hyaluronic acid and pectin were in the state of being complex and were consistent when the concentrations of hyaluronic acid and pectin were above 1 mg/ml and 5 mg/ml respectively, and the mass ratio was 1 : 5. The complex self-assembled to composite grain-shaped film. In comparison with simple hyaluronic acid, the viscosity of hylauronic acid and pectin complex was stronger, and water-solubility was lower. The complex has the bio-function of both hylauronic acid and pectin and has wide application potential in the field of biomedical engineering.