In principle, an electric field via ferroelectric materials can affect the photovoltaic properties, although there is not yet a complete mechanistic understanding. Herein, a built-in electric field without a poling processing step was established by introducing developed PVDF-based ferroelectric additives within active-layer matrices of organic solar cells (OSCs). Upon the existence of the ferroelectric polarization induced by the ferroelectric additives in o-xylene/N-methylpyrrolidone pair featuring halogen-free processing system, high efficiencies of 11.02% and 11.76% are achieved in fullerene and non-fullerene acceptor bulk-heterojunction OSCs, respectively. A comparative study exploring the role of the ferroelectric polarization surrounding the active-layer matrix was also performed using structural, electrical, and morphological techniques, to shed light on the underlying ferroelectric polarization effects on OSCs. Furthermore, the use of the ferroelectric additive is extended to p-n like bilayer OSC to access a rich understanding of the complex enhancement mechanisms afforded by it, demonstrating a highly efficient (11.83%) bilayer device. The above results are fairly comparable to the highest value reported for the recently developed state-of-the-art OSCs processed from halogen-free systems. The use of the ferroelectric additives in the halogen-free system is promising in related organic-semiconductor fields for reasons extending beyond the enhancement of efficiency and the environment-friendly manufacturing.