While the effect of CO2 enrichment on wheat (Triticum spp.) photosynthesis, nitrogen content or yield has been well-studied, the impact of elevated CO2 on metabolic pathways in organs other than leaves is poorly documented. In particular, glumes and awns, which may refix CO2 respired by developing grains and be naturally exposed to higher-than-ambient CO2 mole fraction, could show specific responses to elevated CO2 . Here, we took advantage of a free-air CO2 enrichment experiment and performed multilevel analyses, including metabolomics, ionomics, proteomics, major hormones and isotopes in Triticum durum . While in leaves, elevated CO2 tended to accelerate amino acid metabolism with many significantly affected metabolites, the effect on glumes and awns metabolites was modest. There was a lower content in compounds of the polyamine pathway (along with uracile and allantoin) under elevated CO2 , suggesting a change in secondary N metabolism. Also, cytokinin metabolism appeared to be significantly affected under elevated CO2 . Despite this, elevated CO2 did not affect the final composition of awn and glume organic matter, with the same content in carbon, nitrogen and other elements. We conclude that elevated CO2 mostly impacts on leaf metabolism but has little effect in awns and glumes, including their composition at maturity.