For practical use of perovskite solar cells (PSCs) the instability issues of devices, attributed to degradation of perovskite molecules by moisture, ions migration, and thermal‐ and light‐instability, have to be solved. Herein, highly efficient and stable PSCs based on perovskite/Ag‐reduced graphene oxide (Ag‐rGO) and mesoporous Al2O3/graphene (mp‐AG) composites are reported. The mp‐AG composite is conductive with one‐order of magnitude higher mobility than mp‐TiO2 and used for electron transport layer (ETL). Compared to the mp‐TiO2 ETL based cells, the champion device based on perovskite/Ag‐rGO and SrTiO3/mp‐AG composites shows overall a best performance (i.e., VOC = 1.057 V, JSC = 25.75 mA cm−2, fill factor (FF) = 75.63%, and power conversion efficiency (PCE) = 20.58%). More importantly, the champion device without encapsulation exhibits not only remarkable thermal‐ and photostability but also long‐term stability, retaining 97–99% of the initial values of photovoltaic parameters and sustaining ≈93% of initial PCE over 300 d under ambient conditions.