The initial formation of corrosion products in pure humid air on magnesium alloys AZ91 and AZ31 was studied using infrared reflection absorption spectroscopy (IRRAS), infrared spectroscopic imaging, and SEM-EDS. The kinetics of corrosion product formation were monitored in situ with IRRAS during exposure to humid air (95% relative humidity) under two different CO2 concentrations: low (≤1 ppm) and ambient (400 ppm). For low CO2 concentrations, the primary corrosion product detected on both alloys was magnesium hydroxide (Mg(OH)2). In contrast, under ambient CO2 conditions (400 ppm), magnesium hydroxy carbonate was the dominant product. After 16 h of exposure, the amount of magnesium converted into corrosion products was approximately 8–10 times higher under low-CO2 conditions compared to ambient levels. The smaller formation of corrosion products but increased magnesium carbonate formation on AZ91D is attributed to its higher aluminium content compared to AZ31. Corrosion attack and product formation were largely localised to the centre of the α-phase in AZ91D, with the β-phase likely serving as sites for cathodic reactions.