Waveguide coupling measurements of polymers have largely concentrated on the application of mode analysis to the study of thin supported films (such as spin coatings). The use of prism coupling to study thick, freestanding polymer films, however, has not been reported. In this paper, the ability of prism coupling to characterize the three‐dimensional optical properties of thick, freestanding polymer films and sheets is demonstrated. A modified prism coupling procedure is described that allows the determination of all three principal refractive indices in thick, three‐dimensionally anisotropic freestanding films. A Metricon prism coupler is used in a manner similar to an Abbé refractometer for the measurement of isotactic polypropylene, poly(ethylene terephthalate), PMDA‐ODA polyimide, and poly(phenylene sulfide). Three series of PMDA‐ODA films are also investigated in this study. The first series has been drawn to different extensions from three‐dimensionally random films. The second series has random orientation in the plane of the film but different degrees of planarity with respect to the through direction. The third series are commercial films of varying thickness. These three series of films are compared as to the optical an‐isotropy that is developed from the three different fabrication processes. © 1993 John Wiley & Sons, Inc.