P(VDF/TrFE), a versatile ferroelectric polymer, holds immense promise for diverse applications, but optimizing its ferroelectric properties has been a major bottleneck. We present a groundbreaking approach, demonstrating a remarkable 48% enhancement in polarization through a precise control of the cooling rate after annealing. Slow cooling at 0.5°C/min significantly enhances the β-phase crystallinity, the ferroelectrically active phase, as evidenced by X-ray diffraction. This improved crystallinity directly contributes to the observed polarization enhancement. Dielectric analysis reveals a strong link between cooling rate and molecular alignment, with slower cooling leading to a higher dielectric constant, indicative of superior chain order. This improved order facilitates more efficient polarization switching, further contributing to the enhanced ferroelectricity. Our study unveils the often-overlooked impact of cooling rate on the ferroelectric properties of P(VDF/TrFE) thin films. By manipulating the cooling speed after annealing, we can effectively tailor the material's ferroelectricity, opening new avenues for optimizing device performance and expanding its application potential.