Biodegradable poly (lactic acid) (PLA)/poly (butyleneadipate-co-butyleneterephthalate) (PBAT)/multi-walled carbon nanotube (MWNT) polymer blend nanocomposites were prepared by using a laboratory-scale twin-screw extruder. Fractured surface morphology of the polymer blend/MWNT nanocomposites were examined via SEM. Furthermore, cross sectioned samples obtained using an ultramicrotome was observed via TEM. In addition, effects of both MWNT reinforcement and phase affinity of MWNT on thermal and rheological properties of the PLA/PBAT blends were investigated by TGA and rotational rheometer. Immiscible PLA/PBAT blend with MWNT nanocomposites showed two-step thermal degradation. The onset temperature of thermal degradation started in the PLA much earlier than in the PBAT. Nonetheless, based on TGA data, it was found that the MWNT enhanced thermal property of the PLA/PBAT blend/MWNT nanocomposites. Rheological properties revealed that both shear and complex viscosities showed unique shear thinning behavior due to selectively localized MWNT dispersion state.