Polyvinyl butyral (PVB) films are highly promising materials as they combine interesting thermal and structural morphology properties and in many cases coating viability. However, the polymerization ability of PVB films through solvent casting method using different solvents is fundamentally not well understood. In this rational, the present study demonstrate the use of Isopropanol, ethanol, methanol, and acetic acid for the development of high quality PVB films. The resulting acetic acid-based PVB film exhibits moderated thermal stability with smooth surface morphology which is an important key factor towards coating applications. On the other hand, ethanol-based PVB film achieves higher thermal stability relative to all other PVB films with some structural defects. This study will pave the development of high performance PVB cast films.