Thin film technology has been attracting much interest as a tool for making combinatorial libraries of solid state materials including organic compounds and polymers as well as their devices. Especially, physical vapor deposition is very frequently used in research and development of semiconductors, metals, and advanced ceramics and its coupling with combinatorial chemical concepts has been making remarkable progress and success in recent years. Here we provide a short overview of recent studies on combinatorial fabrication of organic thin film libraries by physical vapor deposition for optimization of their structure and properties for device application.