Three-dimensional (3D) cationic lead halide hybrids constructed by organic ions and inorganic networks via coordination bonds are a promising material for solid-state lighting due to their exceptional environmental stability and broad-spectrum emission. Nevertheless, their fluorescence properties are hindered by the limited lattice distortion from extensive connectivity within the inorganic network. Here, a dramatic 100-fold enhancement of self-trapped exciton (STE) emission is achieved in 3D hybrid material [Pb2Br2][O2C(CH2)4CO2] via pressure-triggered phase transition. Notably, pressure-treated material exhibits a 110 nm redshift with 1.5-fold enhancement compared to the initial state after pressure was completely released. The irreversible structural phase transition intensifies the [PbBr3O3] octahedral distortion, which is highly responsible for the optimization of quenched emission. These findings present a promising strategy for improving the optical properties of 3D halide hybrids with relatively high stability and thus facilitate their practical applications by pressure-driven phase transition engineering.