Nano Ag-deposited BaTiO3 (BT-Ag) hybrid particles usable as fillers for flexible polymeric composites to obtain high dielectric constant, low conductivity, and low dielectric loss were developed. BT-Ag hybrid particles were synthesized via a seed-mediated growing process by a redox reaction between silver nitrate and ethylene glycol. Nano Ag particles with a size less than 20 nm were discretely grown on the surface of the 100 nm BaTiO3. The similar lattice spacing of the (1 1 1) planes of BT and Ag led to the hetero-epitaxial growth of Ag on the BT surface. The thickness of the coherent interface was about 3 nm. The adhesion of Ag to BT efficiently prevented the continuous contact between Ag particles in the polyvinylidene fluoride (PVDF) matrix and suppressed the formation of the conducting path in the composite. As a result, with a filler loading of 43.4 vol %, the composite exhibited a dielectric constant (Dk) value of 94.3 and dielectric loss (tan δ) of 0.06 at 1 kHz. An even higher Dk value of 160 at 1 kHz (16 times larger than that of PVDF) was obtained when the content of BT-Ag was further increased, with low conductivity (σ < 10(-5) S m(-1)) and low dielectric loss (tan δ = 0.11), demonstrating promising applications in the electronic devices.