This paper presents a new methodology based on gas chromatography-mass spectrometry (GCMS) in order to separate and quantify the gases presented inside the cells of rigid polyurethane (RPU) foams. To demonstrate this novel methodology, the gas composition along more than three years of aging is herein determined for two samples: a reference foam and foam with 1.5 wt% of talc. The GCMS method was applied, on one hand, for the accurate determination of C ₅H ₁₀ and CO ₂ cell gases used as blowing agents and, on the other hand, for N ₂ and O ₂ air gases that diffuse rapidly from the surrounding environment into foam cells. GCMS results showed that CO2 leaves foam after 2.5 month (from 21% to 0.03% for reference foam and from 17% to 0.03% for foam with 1.5% talc). C ₅H ₁₀ deviates during 3.5 months (from 28% up to 39% for reference foam and from 29% up to 36% for foam with talc), then it starts to leave the foam and after 3.5 year its content is 13% for reference and 10% for foam with talc. Air diffuses inside the cells faster for one year (from 51% up to 79% for reference and from 54% up to 81% for foam with talc) and then more slowly for 3.5 years (reaching 86% for reference and 90% for foam with talc). Thus, the fast and simple presented methodology provides valuable information to understand the long-term thermal conductivity of the RPU foams.