Fructans, raffinose family oligosaccharides (RFOs) and arabinoxylan oligosaccharides are the main non-digestible oligosaccharides derived from cereals. These non-digestible oligosaccharides are consumed worldwide. They are considered to be acceptable as part of the dietary fiber complex by jurisdictions in North America, Europe and Australia. Fructans and RFOs are naturally present in cereal grains, whereas arabinoxylan oligosaccharides are a product of the hydrolytic degradation of cereal arabinoxylans. This chapter explores the occurrence, synthesis, structures and potential health benefits of fructans and RFOs.