The catalytic transformation of cellulose, the major component of abundant and renewable lignocellulosic biomass, into building-block chemicals is a key to establishing sustainable chemical processes. Cellulose is a polymer of glucose and a lot research effort has been devoted to the conversion of cellulose to six-carbon platform compounds such as glucose and glucose derivatives through CO bond activation. There also exist considerable studies on the catalytic cleavage of CC bonds in biomass for the production of high-value chemicals, in particular polyols and organic acids such as ethylene glycol and lactic acid. This review article highlights recent advances in the development of new catalytic systems and new strategies for the selective cleavage of CC bonds in cellulose and its derived carbohydrates under inert, reductive and oxidative atmospheres to produce C1C5 polyols and organic acids. The key factors that influence the catalytic performance will be clarified to provide insights for the design of more efficient catalysts for the transformation of cellulose with precise cleavage of CC bonds to high-value chemicals. The reaction mechanisms will also be discussed to understand deeply how the selective cleavage of CC bonds can be achieved in biomass.