The present study investigated the effect of various solvents on the tunable surface morphology and photocatalytic activity (PCA) of bismuth oxyiodide (BiOI), which could be used for the reduction of Cr(VI) under visible light irradiation (VLI). BiOI samples exhibiting different morphologies, i.e., two-dimensional square-like nanosheet and three-dimensional hierarchical flower-like morphology, were synthesized by a hydro/solvothermal process using different solvents, namely H2O, MeOH, EtOH, and ethylene glycol (EG). The crystal structure, surface morphology, surface area, light-absorption capability, and recombination rate of the photogenerated charge carriers were examined by X-ray diffraction, scanning electron microscopy, Brunauer–Emmett–Teller analysis, UV–vis diffuse reflectance spectroscopy, photoluminescence, and transient photocurrent analyses, respectively. The BiOI sample fabricated in EG showed excellent photocatalytic efficiency (~99%) for the reduction of Cr(VI) after 90 min under VLI. The enhanced PCA demonstrated that the high surface area and well-structured surface characteristics of flower-like 3D BiOI microspheres played important roles in the photoreduction process. Moreover, a plausible mechanism for the reduction of Cr(VI) over the EG–BiOI photocatalyst was proposed. The results of the PCA evaluation and recycle test revealed that 3D EG–BiOI microspheres could serve as promising materials for the efficient removal of Cr(VI) from wastewater. Additionally, EG–BiOI could be utilized in other environmental remediation processes.