P3HT:PCBM bulk heterojunction solar cells added with ferroelectric polymer were fabricated and characterized. By incorporating P3HT:PCBM solar cell with P(VDF-TrFE) ferroelectric additive, the power conversion efficiency was increased up to nearly 50%. Photoacoustic analysis on this phenomena was carried out for the first time. Through this study, we find that the ferroelectricity of the polymer additive plays the key role in the enhancement of the power conversion efficiency of the organic solar cell by suppressing the non-radiative recombination of charge transfer exciton more effectively.