Extreme nanoconfinement has been shown to significantly affect the properties of materials. Here we demonstrate that extreme nanoconfinement can significantly improve the thermal stability of polystyrene (PS) and reduce its flammability. Capillary rise infiltration (CaRI) is used to infiltrate PS into films of randomly packed silica nanoparticles (NPs) to produce highly confined states. We demonstrate that as the NP size is decreased, increasing the degree of confinement, the isothermal degradation time is dramatically increased, by up to a factor of 30 at 543 K for PS confined in ∼3 nm pores. The activation energy of PS degradation is also increased, by 50 kJ/mol in the most confined state (∼3 nm pores). We demonstrate that the degradation proceeds through the film surface and from the center of large holes toward NP surfaces, indirect evidence that the process is diffusion limited. The surface-driven process dramatically reduces char formation even in large NP packings that show no significant changes in their dynamics and glass transition temperature (Tg) compared to the bulk.