Thin films of silk fibroin were prepared by solvent evaporation from calcium chloride/ethanol aqueous solution. The influence of alcohol treatments on thermal, mechanical and optical properties of silk-fibroin-based film is presented. To understand the conformal structure of the alcohol-treated silk fibroin film, the IR spectral decomposition method is employed. The optical properties especially the optical transparency, haze and fluorescence emission of alcohol-treated silk fibroin film is systematically investigated together with the conformal structure to understand the effect of the fibril such as the beta-sheet influencing the optical properties. Monohydric alcohol treatment increased beta-turn content in the regenerated silk fibroin structure. These affected the amount of light diffusion and scattering within silk-fibroin films. With alcohol-treatment, all the silk-fibroin films exhibit exceptional optical transparency (>90%) with different levels of optical haze (2.56–14.17%). In particular, ethanol-treated silk-fibroin films contain the highest content of beta-turns (22.8%). The ethanol-treated silk-fibroin films displayed a distinct interference of oscillating crests and troughs in the UV-Vis transmittance spectra, thereby showing the lowest optical haze of 2.56%. In contrast, the silk-fibroin films treated with methanol and propanol exhibit the highest (14.17%) and second-highest (10.29%) optical transmittance haze, respectively. The beta-turn content of the silk-fibroin films treated with methanol is the lowest (20.5%). These results show the relationship between the beta-turn content and optical haze properties. The results manifestly provide a method to manufacture exceptional optically transparent silk-fibroin films with adjustable light diffusion and scattering which can be designed to meet specific applications with the potential to provide UV-shielding protection via monohydric alcohol treatment.