Biomass materials have become a research focus for humankind, due to the decreasing availability of fossil fuels and the increasing release of greenhouse gas. In this work, we prepared biodegradable composites with waste cassava residues and polybutylene succinate (PBS) by modifying cassava residues using 4,4’-methylene diisocyanate phenyl ester (MDI) and tested their properties. The effects of MDI modification on the structure, mechanical properties, water absorption, microstructure, and thermal stability of the composites were studied via Fourier transform infrared spectroscopy, contact angle measurement, mechanical property testing, water absorption analysis, scanning electron microscopy, and thermogravimetric analysis, respectively. The results showed that the tensile strength and flexural strength of the material increased by 72% and 20.89%, respectively, when the MDI-modified cassava residue content was 30%. When 10% MDI-modified cassava residues were added, the tensile strength increased by 19.46% from 16.96 MPa to 20.26 MPa, while the bending strength did not change significantly. The water contact angle of the MDI-treated cassava residues exceeded 100°, indicating excellent hydrophobicity. Thus, MDI modification can significantly improve the mechanical properties and thermal stability of the biocomposite. The composites were immersed in distilled water for 96 h. The water absorption of the cassava residues/PBS composite was 2.19%, while that of the MDI-modified cassava residues/PBS composite was 1.6%; hence, the water absorption of the MDI-modified cassava residues/PBS composite was reduced to 26.94%. This technology has wide application potential in packaging, construction, and allied fields.