Application of advanced pyrolysis processes to agricultural waste for liquid production is gaining great attention, especially when it is applied to an economic crop like tobacco. In this work, tobacco residues were pyrolyzed in an ablative reactor under vacuum. The maximum bio-oil yield of 55% w/w was obtained at 600°C with a particle size of 10 mm at a blade rotation speed of 10 rpm. The physical properties of the products showed that the oil produced was of high quality with high carbon, hydrogen, and calorific value. Two-dimensional gas chromatography/time-of-flight mass spectrometric analysis results indicated that the oils were complex mixtures of alkanes, benzene derivative groups, and nitrogen-containing compounds. In addition, 13C NMR results confirmed that long aliphatic chain alkanes were evident. The alkanes were likely converted from furans that were decomposed from hemicelluloses. Ablative pyrolysis under vacuum proved to be a promising option for generating useful amount of bio-oils from tobacco residues.