Poly(vinylidene fluoride) (PVDF) is a kind of important piezoelectric polymer used in spacecraft industry. But the atomic oxygen (AO) is the most abundant element in the low Earth orbit (LEO) environment. AO collision degradation is an important issue in the application of PVDF on spacecrafts. To investigate the erosion behaviors of PVDF during AO impacts and how to improve the stability of PVDF against AO impacts, the temperature evolution, mass loss, and erosion yields of neat PVDF, neat polyhedral oligomeric silsesquioxanes compound (3,3,3-trifluoropropyl)(8)Si8O12 (FP-POSS) and the PVDF/FP-POSS composite under AO impacts, as well as some key disintegrated structures and separated chemical compositions, were researched using the molecular dynamics (MD) simulations and the reactive ReaxFF force field. The simulation erosion yield result of PVDF is very close to the experiment results, which shows our simulations are reliable. The results of the temperature evolution, mass loss, and erosion yield of three materials show that the antierosion performance of PVDF is not outstanding. However, incorporating FP-POSS into PVDF matrix enhances the stability of PVDF against AO impact greatly and reduces the temperature rise, mass loss, and the erosion yield of PVDF rapidly. A detailed analysis on the flight chemical compositions and key snapshots of the structures reveals that the erosion process On PVDF and PVDF/FP-POSS is continuous and should be derived from the same PVDF matrix in two materials. In contrast, the erosion process on FP-POSS is stepped. The erosion will not take place until the number of AO reaches a Specific value. There is a barrier for the erosion of high-energy AO because of the stable cagelike Si-O frame in FP-POSS molecules. This should be chiefly responsible for the high stability of FP-POSS and the reinforcement mechanism of FP-POSS on PVDF against AO impacts. This work is helpful for people to understand the erosion details of PVDF and POSS and provides valuable information to design effective protective structure for PVDF against AO impacts in LEO environment.