LAUSR

Perovskite solar cells in which 2D perovskites are incorporated within a 3D perovskite network exhibit improved stability with respect to purely 3D systems, but lower record power conversion efficiencies (PCEs). Here, a breakthrough is reported in achieving enhanced PCEs, increased stability, and suppressed photocurrent hysteresis by incorporating n‐type, low‐optical‐gap conjugated organic molecules into 2D:3D mixed perovskite composites. The resulting ternary perovskite–organic composites display extended absorption in the near‐infrared region, improved film morphology, enlarged crystallinity, balanced charge transport, efficient photoinduced charge transfer, and suppressed counter‐ion movement. As a result, the ternary perovskite–organic solar cells exhibit PCEs over 23%, which are among the best PCEs for perovskite solar cells with p–i–n device structure. Moreover, the ternary perovskite–organic solar cells possess dramatically enhanced stability and diminished photocurrent hysteresis. All these results demonstrate that the strategy of exploiting ternary perovskite–organic composite thin films provides a facile way to realize high‐performance perovskite solar cells.