The pertinent issue of resources shortage arising from global climate change in the recent years has accentuated the importance of materials that are environmentally friendly. Despite the merits of current material like cellulose as the most abundant natural polysaccharide on earth, the incorporation of lignocellulosic biomass has the potential to value-add the recent development of cellulose-derivatives in drug delivery systems. Lignocellulosic biomass, with a hierarchical structure is comprised of cellulose, hemicellulose and lignin. As an excellent substrate that is renewable, biodegradable, biocompatible and chemically accessible for modified materials, lignocellulosic biomass sets forth a myriad of applications. To date, materials derived from lignocellulosic biomass have been extensively explored for new technological development and applications, such as biomedical, green electronics and energy products. In this review, chemical constituents of lignocellulosic biomass are first discussed before we critically examine the potential alternatives in the field of biomedical application. In addition, the pretreatment methods for extracting cellulose, hemicellulose and lignin from lignocellulosic biomass as well as their biological applications including drug delivery, biosensor, tissue engineering etc. are reviewed. It is anticipated there will be an increasing interest and research findings in cellulose, hemicellulose and lignin from natural resources, which help provide important directions for the development in biomedical applications.