Improved polyvinyl alcohol‐silica replica techniques are described which allow for more accurate examination by electron microscopy of pigment derived microstructure in paint films. These methods complement the silver‐silica techniques which are preferable only for studying much finer details, such as molecular configurations and small distortions of the resinous binder. Procedures have been developed for stripping unaltered baked enamel films from tin plate. The underside of these free films can be examined with the improved replica techniques and it is possible to study differences in top and bottom structure of paint films. Applications of the refined replica techniques in the study of paint films are presented.