In this study, poly(lactic acid) (PLA) and microcrystalline cellulose (MCC)-based green biocomposites were developed using a solution casting technique. Essentially, the bonding between PLA and MCC is quite feeble; therefore, the current study is conducted to strengthen the bonding by incorporating a coupling agent, thereby enhancing the overall quality of the biocomposites. Thus, the present study aimed to examine the influence of combined coupling agents�maleic anhydride (MAH) and maleic acid (MA) (MAH−MA)�on the properties of polylactic acid (PLA)/microcrystalline cellulose (MCC) biocomposites. The investigation also encompassed an examination of the impact of MCC loading (2, 3, and 5% w/w) into a PLA matrix. The Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) examination revealed the interfacial interaction and adhesion among MCC, PLA, and coupling agents and the formation of biocomposites. The incorporation of MAH−MA led to improved mechanical properties of the PLA/MCC biocomposites. Furthermore, the incorporation of MAH−MA into the PLA/3 wt % MCC composite exhibited enhancements in both the tensile strength and tensile modulus, accompanied by a reduced elongation at break. In addition, it is worth noting that the thermogravimetric analysis (TGA) curve of the PLA composite with 3% w/w of MCC and MAH−MA displayed a significant decrease in weight beyond a temperature threshold of 492.65 °C. The water absorption demonstrates that the incorporation of MAH−MA into the PLA/MCC composite led to advantageous water barrier characteristics. The observed improvements were attributed to the efficient dispersion of MCC at the most favorable amount of coupling agents, along with the chemical interactions involving grafting and esterification between MCC and the MAH−MA coupling agent. Furthermore, the incorporation of MAH−MA into the PLA/3% (w/w) MCC composite exhibited enhancements in both the tensile strength and tensile modulus, accompanied by a reduction in the elongation percentage at break. The experimental results about water absorption demonstrate that the incorporation of MAH−MA into the PLA/MCC composite led to advantageous water barrier characteristics. These improvements were attributed to good MCC dispersion and the chemical interactions involving grafting and esterification between the MCC and the MAH−MA coupling agent.