Bismuth oxyiodide (BiOI) has attracted much attention as a kind of novel functional material because of its highly anisotropic crystal structure and promising optical properties. However, the low photoenergy conversion efficiency of BiOI highly limits its practical applications owing to its poor charge transport. Tailoring the crystallographic orientation has emerged as an effective way to modulate the charge transport efficiency, while there is nearly no report on BiOI. In this study, (001)- and (102)-oriented BiOI thin films were synthesized for the first time with mist chemical vapor deposition at atmospheric pressure. The photoelectrochemical response for the (102)-oriented BiOI thin film was much better than that of the (001)-oriented thin film, owing to the enhanced charge separation and transfer efficiency. The intensive surface band bending and larger donor density for (102)-oriented BiOI were the main origins of the efficient charge transport. Besides, the BiOI-based photoelectrochemical-type photodetector exhibited excellent photodetection performance with a high responsivity of 78.33 mA W-1 and a detectivity of 4.61 × 1011 Jones for visible light. This work provided fundamental insights into anisotropic electrical and optical properties in BiOI, which would be beneficial for the design of bismuth mixed-anion compound-based photoelectrochemical devices.