Chitosan (CH) and pectin (PE) are considered as promising biomaterials in developing eco-friendly films due to their film-forming, biodegradable, and non-toxic characteristics, the films from pure CH or PE have obvious defects such as poor barrier and mechanical properties. In this study, the blend films of CH and PE at varying mass ratios were characterized. Structurally, numerous small pores evenly distributed in PE film while big caves unevenly scattered in CH film. CH film is semicrystalline but PE and blend films are totally amorphous, the two individual films presented comparable values in water content and solubility to blend films. The CH film showed lower water vapor permeability and surface wettability and these parameters of the blend films decreased with CH level, the blend films exhibited high transparence as PE film did, which is much higher than that of CH film. Mechanically, the PE film presented higher values in stretchability and tensile strength than CH film. Moreover, in a different blending ratios, synergistic effects were found with several characters of the CH/PE blend film, especially in transparence and mechanical properties. These synergistic effects were ascribed to the intermolecular electrostatic interactions between CH and PE.