Chemical doping represents a crucial and effective approach for controlling electricity and also many other properties, but the underlying mechanisms connecting dopant-induced structural evolutions to emergent functionalities remain incompletely understood. To address this knowledge gap, the atomic-level mechanism of the enhanced electric polarization in a typical perovskite ferroelectric oxide BiFeO₃ (BFO) is unveiled. B-site Mn-dopping, with bringing about atomic-level lattice and charge evolutions, clearly accelerates the local lattice distortion i.e. enhanced Fe/Mn displacement and (Fe/Mn)O₆ octahedral rotation. This facilitates large-scale polarization orientation alignment to create the enhanced collective polarity while manifesting an overall ferroelectric polarization of up to ~160 μC/cm². Local lattice distortion also promotes the Jahn-Teller effect because of the increasing proportion in Mn³⁺ (3d⁴ configuration) that could instigate symmetry-breaking stretching and bending distortions of (Fe/Mn)O₆ octahedra with showing improved magnetic moments. Our findings uncover the ferroelectricity-enhanced origination and offer a new paradigm for principally designing ferroelectric functions.