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Abstract 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. 

Abstract 2D polymers (2DPs) are promising as structurally well‐defined, permanently porous, organic semiconductors. However, 2DPs are nearly always isolated as closed shell organic species with limited charge carriers, which leads to low bulk conductivities. Here, the bulk conductivity of two naphthalene diimide (NDI)‐containing 2DP semiconductors is enhanced by controllably n‐doping the NDI units using cobaltocene (CoCp₂). Optical and transient microwave spectroscopy reveal that both as‐prepared NDI‐containing 2DPs are semiconducting with sub‐2 eV optical bandgaps and photoexcited charge‐carrier lifetimes of tens of nanoseconds. Following reduction with CoCp₂, both 2DPs largely retain their periodic structures and exhibit optical and electron‐spin resonance spectroscopic features consistent with the presence of NDI‐radical anions. While the native NDI‐based 2DPs are electronically insulating, maximum bulk conductivities of >10⁻⁴ S cm⁻¹are achieved by substoichiometric levels of n‐doping. Density functional theory calculations show that the strongest electronic couplings in these 2DPs exist in the out‐of‐plane (π‐stacking) crystallographic directions, which indicates that cross‐plane electronic transport through NDI stacks is primarily responsible for the observed electronic conductivity. Taken together, the controlled molecular doping is a useful approach to access structurally well‐defined, paramagnetic, 2DP n‐type semiconductors with measurable bulk electronic conductivities of interest for electronic or spintronic devices.