A novel method was developed for the sampling of volatiles produces by polymer decomposition during UL94 standard flammability tests, allowing to collect, separate and analyze the precise composition of the fuel mixture feeding the flame in the real flammability tests. The system was validated on epoxy resin/polyhedral oligomeric silsesquioxanes and found extremely informative for the understanding of the flame retardancy mechanisms of POSS, previously referred to as the "blowing-out effect". Collected products were analyzed by infrared spectroscopy and gas chromatography/mass spectroscopy, to identify the gaseous and liquid decomposition products, allowing to depict a comprehensive decomposition pathway for the epoxy resin. Lightweight volatiles, gaseous at room temperature, showed limited differences as a function of DOPO-POSS, whereas mixtures of liquid products evidenced for dramatic changes in the relative concentration as a function of DOPO-POSS. In pristine epoxy resin, the most abundant products were recognized as benzene, phenol, naphthalene and toluene, along with several tens of other aromatic products observed in lower amounts. The presence of DOPO-POSS at low concentration (2.5%) radically changes the composition of the aromatic volatiles mixture, as no significant amount of benzene is produced, while phenol becomes the main product, accounting for about half of the total, isopropyl phenol and bisphenol A, along with several tens of other products in lower concentrations. Such modification of the fuel mixture feeding the flame provided an explanation for the lower flammability of this formulation, as well as for the phenomenology of the blowing out effect.Keywords: epoxy resin decomposition mechanism; DOPO-POSS; blowing-out effect; sampling of volatiles during flame test, fuel mixture in flammability tests