Polysaccharides constitute the largest fraction of biomass. With the upsurge of interest in utilization of biomass as a renewable resource for fuels and chemicals via the fast pyrolysis route, studying carbohydrate pyrolysis is of key importance. Several researchers have presented pyrolysis models that can predict the yields of overall char, bio-oil and gaseous fractions; however, models have yet to be developed that can predict the more detailed composition of the bio-oil. Furthermore, little work has been done to distinguish between the products of primary and secondary reactions. In the present study, several mono-, di- and polysaccharides, varying in the position and orientation of glycosidic linkages, were pyrolyzed under conditions that minimized secondary reactions. The product distribution from the pyrolysis of these polysaccharides tells us that α or β orientation of the glycosidic linkage has negligible effect on the product distribution, however the position of linkage has a significant impact on product yields.