Inorganic cesium lead iodide perovskite CsPbI3 is attracting great attention as a light absorber for single or multi‐junction photovoltaics due to its outstanding thermal stability and proper band gap. However, the device performance of CsPbI3‐based perovskite solar cells (PSCs) is limited by the unsatisfactory crystal quality and thus severe non‐radiative recombination. Here, vacuum‐assisted thermal annealing (VATA) is demonstrated as an effective approach for controlling the morphology and crystallinity of the CsPbI3 perovskite films formed from the precursors of PbI2, CsI, and dimethylammonium iodide (DMAI). By this method, a large‐area and high‐quality CsPbI3 film is obtained, exhibiting a much reduced trap‐state density with prolonged charge lifetime. Consequently, the solar cell efficiency is raised from 17.26 to 20.06 %, along with enhanced stability. The VATA would be an effective approach for fabricating high‐performance thin‐film CsPbI3 perovskite optoelectronics.