Developing a green and sustainable method to upgrade biogas wastes into high value-added products is attracting more and more public attention. The application of solid residues as a performance enhancer in the manufacture of biofilms is a prospective way to replace conventional plastic based on fossil fuel. In this work, solid digestates from the anaerobic digestion of agricultural wastes, such as straw, cattle and chicken manures, were pretreated by an ultrasonic thermo-alkaline treatment to remove the nonfunctional compositions and then incorporated in plasticized starch paste to prepare mulching biofilms by the solution casting method. The results indicated that solid digestate particles dispersed homogenously in the starch matrix and gradually aggregated under the action of a hydrogen bond, leading to a transformation of the composites to a high crystalline structure. Consequently, the composite biofilm showed a higher tensile strength, elastic modulus, glass transition temperature and degradation temperature compared to the pure starch-based film. The light, water and GHG (greenhouse gas) barrier properties of the biofilm were also reinforced by the addition of solid digestates, performing well in sustaining the soil quality and minimizing N2O or CH4 emissions. As such, recycling solid digestates into a biodegradable plastic substitute not only creates a new business opportunity by producing high-performance biofilms but also reduces the environmental risk caused by biogas waste and plastics pollution.