Photovoltaic performances of the bismuth-based solar cells are profoundly affected by the thin film quality of the photoactive layer. Herein, we report on various green solvent system to obtain the highly crystalline, pinhole free and homogeneously methylammonium bismuth iodide (MBI) active layer. The MBI structure prepared with tetrahydrofuran:2-ethoxy-ethanol (THF-2ETO) solvent system was found to have the best film quality. Adding 0.05 M 2ETO as the co-solvent is sufficient to produce high quality BiI3 and MBI thin films. According to the Xray photoelectron spectroscopy (XPS) analyzes, we have demonstrated that there is an interaction between BiI3 and 2ETO according to the concentration of 2ETO added to the main THF. Our study clarifies the importance of THF-2ETO solvent system that can accelerate the evolution of the Bi-based solar cells by creating high-quality BiI3 or MBI thin films.