Polypropylene (PP) foam has a great deal of application since it normally exhibits non-uniform cell size distribution, low cell density, and cracked cells. In this study, a small amount of fluoroelastomer (FKM) was used as a nucleating agent to prepare well-defined microporous PP foam by supercritical CO2. It was observed that solid FKM was present as the nanoscale independent phase in PP matrix and the FKM could induce a mass of CO2 aggregation, which significantly enhanced the diffusion rate of CO2 in PP. The resultant PP/FKM foams exhibited much smaller cell size (~24 μm), and more than 16 times cell density (3.2×108 cells/cm3) as well as a much more uniform cell size distribution than that of the neat PP foam. PP/FKM foams possessed major concurrent enhancement in their tensile stress and compressive stress compared to neat PP foam. We believed that the added FKM played a key role in enhancing the heterogeneous nucleation, combined with the local strain field variation in the multiple-phase system, which was responsible for the considerably improved cell morphology of PP foaming. This paper provides a deep understanding of the scCO2 foaming behavior of PP in the presence of FKM.