We expect satellites at altitude below 300 km, very low Earth orbit (VLEO), making observations of the Earth at optical wavelength with increasingly higher resolution. The density of atomic oxygen (AO) at VLEO is significantly higher than that at LEO; severe degradation of spacecraft materials (polymers) due to the high-flux AO is a serious concern. To clarify VLEO environmental effects on spacecraft materials, we designed the Material Degradation Monitor (MDM) and MDM2 missions. The MDM is a material exposure experiment onboard the Super Low-Altitude Test Satellite (SLATS). It aims to understand reactions and degradation of polymeric materials depending on AO fluence in VLEO. In the MDM, samples of spacecraft material were exposed at altitude of 160–560 km; their degradation behaviors were observed optically by a CCD camera for 1.8 years. The MDM2 is a material exposure experiment onboard the International Space Station (ISS) and aims to correctly understand surface reactions and degradation of the same samples used in the MDM at a given AO fluence. In the MDM2, the samples were exposed at altitude of 400 km for 1 year and then returned to Earth for analysis. Based on the results from both missions, we will help in the molecular design of more-durable materials, and establish design standards for future VLEO satellites. This study aims to quantitatively understand the surface reactions and degradation of the 11 types of thermal control materials exposed on the ISS in the MDM2. Five types of multilayer insulation (MLI) films (three types of Si-containing AO protective materials (a silsesquioxane-(SQ-) containing coated polyimide film, two types of polysiloxane-block polyimide (BSF-30) films), an ITO-coated polyimide film, and a Beta Cloth), and flexible optical solar reflectors (flexible OSRs) were found to have a high durability against erosion by AO. This was determined by measuring their loss of mass and thermo-optical properties. The Ag/Inconel layer’s discoloration and peeling were observed for three types of FEP/Ag films as determined by the Ag layer’s oxidation by AO. Also, X-ray photoelectron spectroscopy (XPS) showed that reactions of the Si-containing materials, the SQ-coated polyimide film and the BSF-30 film, form a layer of silica that protects against AO. Even though the concentration of Si in the SQ-coating is the same or greater than in the BSF-30 film, the amount of the SQ-coating that reacted was larger than that of the BSF-30 film under the same AO fluence. Moreover, the effective ability of the UV-shielding coating, composed of ITO and CeO2 coated onto one of the BSF-30 films, was demonstrated by UV–Vis spectrometry. Its sufficient AO protection was confirmed by mass measurements, XPS analyses, and FE-SEM observations.