Upgrading of biomass pyrolysis vapors over 20 wt.% Na2CO3/γ-Al2O3 catalyst was studied in a lab-scale fix-bed reactor at 500 °C. Characterization of the catalyst using SEM and XRD has shown that sodium carbonate is well-dispersed on the support γ-Al2O3. TGA and 23Na MAS NMR suggested the formation of new hydrated sodium phase, which is likely responsible for the high activity of the catalyst. Catalytic oil has much lower oxygen content (12.3 wt.%) compared to non-catalytic oil (42.1 wt.%). This comes together with a tremendous increase in the energy density (37 compared to 19 MJ kg−1). Decarboxylation of carboxylic acids was favoured on the catalyst, resulting to an oil almost neutral (TAN = 3.8 mg KOH/g oil and pH = 6.5). However, the mentioned decarboxylation resulted in the formation of carbonyls, which correlates to low stability of the oil. Catalytic pyrolysis results in a bio-oil which resembles a fossil fuel oil in its properties.