A simple and facile stereolithography 3D printing technique was utilized to fabricate piezoelectric photopolymer-based polyvinylidene fluoride (PVDF) blends. Different process variables, such as solvent (N,N-dimethylformamide, DMF) to PVDF ratio and PVDF solution to photopolymer resin (PR) ratio, were engineered to enhance the dispersion of the PVDF into the PR so as to achieve the maximum piezoelectric coupling coefficient. Our results demonstrate that a ratio of 1:10 (PVDF:DMF) and 2 wt%-PVDF/PR was optimal for the best dissolution of the PVDF, 3D printability, and piezoelectric properties. Under these conditions, the blend generated ±0.121 nA under 80 N dynamic loading excitation. We believe that the findings of this work would promote many further studies on the mass production of flexible piezoelectric polymer blends with higher quality finished surface and design flexibility.