Poly(vinylidene fluoride)-based dielectric materials are prospective candidates for high power density electric storage applications because of their ferroelectric nature, high dielectric breakdown strength and superior processability. However, obtaining a polar phase with relaxor-like behavior in poly(vinylidene fluoride), as required for high energy storage density, is a major challenge. To date, this has been achieved using complex and expensive synthesis of copolymers and terpolymers or via irradiation with high-energy electron-beam or γ-ray radiations. Herein, a facile process of pressing-and-folding is proposed to produce β-poly(vinylidene fluoride) (β-phase content: ~98%) with relaxor-like behavior observed in poly(vinylidene fluoride) with high molecular weight > 534 kg mol⁻¹, without the need of any hazardous gases, solvents, electrical or chemical treatments. An ultra-high energy density (35 J cm⁻³) with a high efficiency (74%) is achieved in a pressed-and-folded poly(vinylidene fluoride) (670-700 kg mol⁻¹), which is higher than that of other reported polymer-based dielectric capacitors to the best of our knowledge.