Dion-Jacobson (DJ) quasi-2D perovskite solar cells (PSCs) have received increasing attention due to their greater potentials in realizing efficient and stable quasi-2D PSCs relative to their Ruddlesden-Popper counterpart. The substitution of methylammonium (MA+) with formamidinium is expected to be able to further increase the stability and power conversion efficiency (PCE) of DJ quasi-2D PSCs. Herein, we report a multifunctional additive strategy for preparing high-quality MA-free DJ quasi-2D perovskite films, where 1,1′-carbonyldi(1,2,4-triazole) (CDTA) molecules are incorporated into the perovskite precursor solution. CDTA modification can control phase distribution, enlarge grain size, modulate crystallinity and crystal orientation, and passivate defects. After CDTA modification, more favorable gradient phase distribution and accordingly gradient band alignment are formed, which is conducive to carrier transport and extraction. The improved crystal orientation can facilitate carrier transport and collection. The enlarged grain size and effective defect passivation contribute to reduced defect density. As a result, the CDTA-modified device delivers a PCE of 16.07%, which is one of the highest PCEs ever reported for MA-free DJ quasi-2D PSCs. The unencapsulated device with CDTA maintains 92% of its initial PCE after aging under one sun illumination for 360 h and 86% after aging at 60 °C for 360 h.