Two-dimensional (2D) CsPb2Br5 exhibits intriguing functions in enhancing the performance of optoelectronic devices in terms of environmental stability and luminescence properties when composited with other perovskites in different dimensionalities. We built a type I three-dimensional (3D) CsPbBr3/2D CsPb2Br5 heterojunction through phase transition where CsPbBr3 quantum dots in situ grew into 2D CsPb2Br5. A thorough growth mechanism study in combination with excited state dynamic investigations via femtosecond spectroscopy and first-principles calculations revealed that the type I hierarchy enhanced the stability of the heterojunction and spurred its luminous quantum yield by prolonging the lifetime of photogenerated carriers. Mixing the heterojunction with other phosphors yielded white-light-emitting diodes with a color rendering index of 94%. The work thus not only offered one new avenue for building heterojunctions by using the "soft crystal" nature of perovskites but also disentangled the enhanced luminescence mechanism of the heterojunction that can be harnessed for promising applications in the luminescence and display fields.