Organic-inorganic perovskites face the issues of being vulnerable to oxygen and moisture and the trap sites located at the surface and grain boundaries. Integration of two-dimensional (2D) perovskites as a capping layer is an effective route to enhance both photovoltaic efficiency and environmental stability of the three-dimensional (3D) underlayer. Here, we employ 1,4-butanediammonium diiodide (BDADI), which has a short chain length and diammonium cations, to construct a 3D/2D stacking perovskite solar cells (PSCs). The introduction of BDA2+ could passivate surface defects in 3D perovskites by forming 2D Dion-Jacobson (DJ) phase perovskites and effectively suppressing nonradiative recombination, thus resulting in a longer carrier lifetime. The DJ 2D capping layer also regulate the energy level arrangement, enabling a better charge extraction and transport process. In addition, the water-resistance ability of 3D perovskite gets improved because of the hydrophobic characteristic of 1,4-butanediammonium cations. Consequently, the 3D/2D stacking PSCs yield an energy conversion efficiency of 20.32% in company with the enhanced long-term stability.