Vibrational piezoelectric energy harvesters are being investigated to replace batteries in embedded sensor systems. The energy density that can be harvested depends on the figure of merit, d₃₃g₃₃, where d₃₃ and g₃₃ are the piezoelectric charge and voltage coefficient. Commonly used piezoelectric materials are based on inorganic ceramics, such as lead zirconium titanate (PZT), as they exhibit high piezoelectric coefficients. However, ceramics are brittle, leading to mechanical failure under large cyclic strains and, furthermore, PZT is classified as a Substance of Very High Concern (SVHC). To circumvent these drawbacks, we fabricated quasi 1–3 potassium sodium lithium niobate (KNLN) ceramic fibers in a flexible polydimethylsiloxane (PDMS) matrix. The fibers were aligned by dielectrophoresis. We demonstrate for the structured composites values of d₃₃g₃₃ approaching 18 pm³ J⁻¹, comparable to that of state-of-the-art ceramic PZT. This relatively high value is due to the reduced inter-particle distance in the direction of the electric field. As a confirmation, the stored electrical energy for both material systems was measured under identical mechanical loading conditions. The similar values for KNLN/PDMS and PZT demonstrate that environmentally friendly, lead-free, mechanically compliant materials can replace state-of-the-art environmentally-less-desirable ceramic materials in piezoelectric vibrational energy harvesters.