Poly(vinylidene fluoride) (PVDF) is a piezoelectric and thermoplastic material with great potential for additive manufacturing (AM) applications. Using barium titanate (BaTiO₃) as filler, PVDF-based composite materials were developed, characterized, and processed by AM material extrusion (MEX). The morphological features and phase transformations occurring throughout the processing of BaTiO₃-filled PVDF, from the compounding to the printed part, were analyzed. The morphology of the powder feedstock after dispersion in a high-energy ball mill changed from spheroidal to laminar and β-phase formation was favored. Microhardness gradually increased with the BaTiO₃ content, obtaining an enhancement of ~60% for a content of 25 vol%, and supported the good dispersion of the filler. A ~48% increase of the dielectric permittivity was also achieved. After extrusion, filaments with a filler content of 15 vol% showed a more stable diameter, as well as higher crystallinity and surface roughness, compared with those with lower BaTiO₃ contents. Material extrusion of filament and direct printing of pellets based on MEX were successfully used to obtain AM parts. Composite parts showed enhanced surface roughness, hydrophilicity, and flexural modulus (up to ~33% for the 7 vol% composite compared with the PVDF), thus leading to superior mechanical characteristics and potential biomedical applications.