Organic–inorganic hybrid perovskite has attracted extensive research due to its excellent optoelectronic properties and is a competitive candidate material for a new generation of photodetectors. However, lateral structure photodetectors based only on perovskite active materials still present moderate performance and poor stability. Herein, lateral structure formamidinium‐based perovskite FA0.9Cs0.1PbI3 photodetectors are reported which are modified by a solution‐processed organic semiconductor 2,7‐dioctyl[1]benzothieno[3,2‐b][1]benzothiophene (C8‐BTBT) layer for improved photosensitive performance and ambient/flexibility stability. High‐mobility organic semiconductor C8‐BTBT serves as an efficient hole transport layer that fills the grain boundaries and gaps of the FA0.9Cs0.1PbI3 film, enabling rapid extraction and transport of the photo‐generated carriers from the perovskite to the electrodes, resulting in enhanced photosensitive performance of the photodetector. Compared with the original device, the C8‐BTBT‐modified photodetector exhibits dramatically improved performance with a best responsivity of 1278 mA W−1, specific detectivity of 1.58 × 1012 Jones, external quantum efficiency of 298%, and fall time of 14.09 ms, which is 10.84 times less than 152.76 ms of the pure perovskite device. Moreover, the C8‐BTBT film acts as a protective layer for the FA0.9Cs0.1PbI3 film because of its good air stability and effective coverage, which significantly improves the ambient stability of the perovskite photodetector compared with the original device, increasing photocurrent retention from 2.5% to 61.5% or 81.5% at different humidity after 6 days. Furthermore, the C8‐BTBT‐modified perovskite photodetector exhibits outstanding flexibility performance, with only a 5% reduction in photocurrent under bending and almost no change after 200 bending cycles, while those of the pristine perovskite device have degraded to ≈80% and ≈75% under the same conditions, respectively. This study provides a facile and effective solution‐processed‐based strategy for constructing high‐performance and stable perovskite photodetectors.
