The interest in xylitol has increased considerably in recent years, due to many commercial applications in different industrial sectors like food, dental related products, and pharmaceuticals. As industrial biotechnological routes to xylitol are costly they currently represents a small fraction of the marketshare. Therefore, over the past few decades much effort has been devoted to the development of cost-effective and environmentally-friendly biotechnological processes by evaluating cheaper lignocellulosic substrates. In this chapter, xylitol commercial processes, cost and market trends are discussed with a special focus on biorefining and biotechnological methods. Increasing commercial and scientific interest in xylitol has led to a strong demand for this product in the global market, of more than 125,000 tons per anum, with a value that is relatively high (4.5–5.5$/kg for bulk purchase by pharma/chewing gum companies and 12£ or 20$/kg in supermarkets) makes its an attractive proposition for commercialization.