Processing bio-oil with the help of currently existing petroleum refinery infrastructure has been considered as a promising alternative to produce sustainable fuels in the future. The feasibility of bio-oil production and upgrading processes depend upon its chemical composition which in turn depends on the biomass composition and the process conditions of the fast pyrolysis reactions. The primary goal of this paper was to investigate the effect of mineral salts including mixtures of salts in the form of switchgrass ash on the chemical speciation resulting from primary pyrolysis reactions of cellulose and to gain an insight of the underlying mechanisms. Various concentrations of inorganic salts (NaCl, KCl, MgCl(2), CaCl(2), Ca(OH)(2), Ca(NO(3))(2), CaCO(3) and CaHPO(4)) and switchgrass ash were impregnated on pure cellulose. These samples were pyrolyzed in a micro-pyrolyzer connected to a GC-MS/FID system. Effects of minerals on the formation of (a) low molecular weight species - formic acid, glycolaldehyde and acetol, (b) furan ring derivatives - 2-furaldehyde and 5-hydroxy methyl furfural and (c) anhydro sugar - levoglucosan are reported exclusively. Further, the effect of reaction temperature ranging from 350 to 600 degrees C on the pyrolysis speciation of pure and ash-doped cellulose is also reported. The pyrolysis speciation revealed the competitive nature of the primary reactions. Mineral salts and higher temperatures accelerated the reactions that led to the formation of low molecular weight species from cellulose as compared to those leading to anhydro sugars.