Cellulose nanowhiskers (CNW), extracted from ramie fibers by sulfuric acid hydrolysis, were used as substrates to compatibilize binary polyester blends containing 50/50 (w/w) polycaprolactone (PCL) and polylactide (PLA). To tailor their interfacial energy and fine-tune their adhesion with the components of the blend, CNW were subjected to different surface polyester grafting by the means of ring-opening polymerization. PCL and PLA homopolyesters as well as P(CL-b-LA) diblock copolymers were successfully grafted on the surface of CNW and the resulting substrates were loaded into the PCL/PLA blend by melt-blending. Morphological and rheological analyses were conducted in order to evaluate the ability of these nanoparticles to enhance the compatibility of PCL/PLA blends. Our results showed that unmodified CNW as well as (co)polyester-grafted CNW improved, at different levels, the compatibility of PCL/PLA blends by preventing from coalescence the dispersed domains. (co)polyester-grafted CNW also enhance the mechanical properties of the blend, which can be explained by the formation of cocontinuous phase morphology at the interface. Our findings suggest that (co)polyester-grafted CNW, especially CNW-g-P(CL-b-LA) diblock copolymers, can serve as a suitable nanofiller to tune the compatibility of PCL/PLA blends and their related microstructures.