Carbonation of alkali activated materials is one of the main deteriorations affecting their durability. However, current understanding of the structural alteration of these materials exposed to an environment inducing carbonation at the nano/micro scale remains limited. This study examined the evolution of phase assemblages of alkali activated slag mortars subjected to accelerated carbonation (1% CO2, 60% relative humidity, up to 28 day carbonation) using XRD, FTIR and 29Si, 27Al, and 23Na MAS NMR. Samples with three water to binder (w/b) ratios (0.35, 0.45, and 0.55) were investigated. The results show that the phase assemblages mainly consisted of C-A-S-H, a disordered remnant aluminosilicate binder, and a minor hydrotalcite as a secondary product. Upon carbonation, calcium carbonate is mainly formed as the vaterite polymorph, while no sodium carbonate is found after carbonation as commonly reported. Sodium acts primarily as a charge balancing ion without producing sodium carbonate as a final carbonation product in the 28-day carbonated materials. The C-A-S-H structure becomes more cross-linked due to the decalcification of this phase as evidenced by the appearance of Q4 groups, which replace the Q1 and Q2 groups as observed in the 29Si MAS NMR spectra, and the dominance of Al(IV) in 27Al MAS NMR. Especially, unlike cementitious materials, the influence of w/b ratio on the crystalline phase formation and structure of C-A-S-H in the alkali activated mortars before and after carbonation is limited.