PVDF as a novel material used in space was badly affected by atomic oxygen from Low Earth Orbit. Some results have been obtained that mechanical and polarization properties can be remarkably increased and ensured by addition of POSS. This article provides a comprehensive overview of the atomic oxygen erosion process of POSS/PVDF composites simulated using Monte Carlo method. The influence of POSS addition on PVDF matrix and the reinforcing mechanism of POSS on PVDF were analyzed. The models of POSS/PVDF composite undergo different years of atomic oxygen erosion were constructed. The relationship between the initial defect size and the erosion effect was also derived. (C) 2014 Elsevier B.V. All rights reserved.