Bismuth-based ternary compounds have attracted much attention owing to their various merits, such as low toxicity and tunable electrical and optical properties. However, these compounds are yet to be understood due to the lack of suitable targets limited by immature synthesis techniques. In this work, we aimed at the synthesis, properties investigation, and photodetection application of Bi13S18I2. Mist chemical vapor deposition was adopted for the deposition of the Bi13S18I2 thin film for the first time. The deposition mechanism was discussed from the perspective of crystal phase and surface morphology. Based on the Bi13S18I2 thin film synthesized at optimal temperature, we constructed a photoelectrochemical-type photodetector. The photodetection performance was evaluated from the points of electrolyte composition, working temperature, and bias voltage. This study would pave the way for the controllable synthesis and applications of bismuth-based ternary compounds.