Generally, the 2D CsPbI3 layer capping on 3D counterparts has been considered as an effective strategy for both enhancing photovoltaic efficiency and stability. However, the intrinsically poor out-of-plane charge transport through the 2D layer remarkably hinders the overall performance of solar devices. To overcome such a challenge, we report the rationally designed 3D-CsPbI3/2D-(PYn)PbI4 (n = 1–4) heterojunctions with desirable energy level matching. It is evidenced that the valence band (VB) edge reconfiguration would occur with the increase of n, accompanied by the VB maximum (VBM) of the 2D component moving down from the higher level above that of the 3D component to the underneath. Consequently, the as-constructed 3D/2D-(PYn)PbI4 (n = 1, 2) heterojunctions exhibit optimal energy level matching, with accelerated transport of holes from 3D to 2D component and limited backflow of electrons. These findings might provide some meaningful insights on the energy level matching in 3D/2D perovskite heterojunctions.