In this study, polylactic acid (PLA)/polyvinylidene fluoride (PVDF) blends were fabricated via solution casting. To eliminate the adverse effect of moistureinduced phase separation, the samples were dried at 60℃. The accelerated drying also reduced the phase separation between the blend components leading to a smaller size of the dispersed phase, i.e., increased interfacial area. Morphology results revealed that, in contrast to PVDF, PLA exhibits a more uniform distribution once used as the dispersed phase. The ratio of β to α crystals in PVDF was increased upon the introduction of PLA. On the other hand, the crystallized PVDF domains improved the PLA crystallinity. Rheological analysis indicated that the viscoelastic response of the 50/ 50 blend was governed by the PVDF phase, which agreed with the fact that PVDF became the matrix phase in that composition. The samples with PVDF as the matrix exhibited a shear-thinning behavior instead of the partial Newtonian behavior of blends with PLA as the matrix. The dynamic mechanical analysis results, further proved our claims from rheological measurements. The damping curves suggested that PVDF as the dispersed phase caused a higher restricting effect on the macromolecular motions, attributed to its dispersion quality. The wettability results showed an increasing trend in the hydrophobicity as the PVDF content increased in the blends. Due to the enhanced β phase content and improved compatibility, PLA/PVDF blends with 30/70 and 50/ 50 compositions show a promising potential to be used in piezoelectric devices.