A total of thirty-one samples were included in the National Aeronautics and Space Administration (NASA) Glenn Research Center (GRC) Polymer Film Thermal Control (PFTC) and Gossamer Materials experiments, which were exposed to the low Earth orbit environment for nearly 4 years on the exterior of the International Space Station (ISS) as part of the Materials International Space Station Experiment (MISSE 1 and MISSE 2). This paper describes objectives, materials, and characterizations for the MISSE 1 and MISSE 2 GRC PFTC and Gossamer Materials samples. Samples included films of polyimides, fluorinated polyimides, and Teflon® fluorinated ethylene propylene (FEP) with and without second-surface metalized layers and/or surface coatings. Films of polyphenylene benzobisoxazole (PBO) and a polyarylene ether benzimidazole (TOR-LM TM) were also included. Polymer film samples were examined post-flight for changes in mechanical and optical properties. The environment in which the samples were located was characterized through analysis of sapphire contamination witness samples and samples dedicated to atomic oxygen (AO) erosion measurements. Results of the analyses of the PFTC and Gossamer Materials experiments are discussed.