2D Ruddlesden-Popper perovskites (RPPs) have attracted extensive attention in recent years due to their excellent environmental stability. However, the power conversion efficiency (PCE) of RPP solar cells is much lower than that of 3D perovskite solar cells (PSCs), mainly attributed to their poor carrier transport performance and excessive heterogeneous phases. Herein, the binary spacers (n-butylammonium, BA and benzamidine, PFA) are introduced to regulate the crystallization kinetics and n-value phase distribution to form uniform phase permutation of RPP films. The study then incorporates n = 5 BA₂MA₄Pb₅I₁₆ memory single crystal to achieve ultrafast stepped-type carrier transport from the low n-value phases to the high n-value phases in the high-quality (BA_0.75PFA_0.25)₂MA₄Pb₅I₁₆ films. These binary spacers and single-crystal-assisted crystallization strategies produce high-quality films, leading to fast carrier extraction and significant nonradiative recombination suppression. The resulting PSC presents a champion PCE of 21.15% with an impressive open circuit voltage (V_OC) of 1.26 V, which is the record high efficiency and V_OC for low n-value RPP solar cells (n ≤ 5).