Layered 2D perovskites have been extensively investigated by scientists with photovoltaics (PV) expertise due to their good environmental stability. However, a random phase distribution in the perovskite film could affect both the performance and stability of the devices. To overcome this problem, we propose multifunctional interface engineering of 2D GA(2)MA(4)Pb(5)I(16) perovskite by employing guanidinium bromide (GABr) on top of it to optimize the secondary crystallization process. It is found that GABr treatment can facilitate to form a shiny and smooth surface of the 2D GA(2)MA(4)Pb(5)I(16) film with excellent optoelectronic properties. Thus, we realize efficient and stable 2D perovskite solar cells (PSCs) with a champion power conversion efficiency (PCE) of 19.3% under AM 1.5G illumination. Additionally, the optimized device without encapsulation could retain 94% of the initial PCE for more than 3000 h after being stored under ambient conditions.