The recent focus in the field of biomaterials has been on the design of intelligent materials. Toward this goal, materials have been developed, which can provide specific bioactive signals to control the biological environment around them during the process of materials integration and wound healing. In addition, materials have been developed that can respond to changes in their environment, such as a change in pH or cell‐associated enzymatic activity. In designing such novel biomaterials, researchers have sought not merely to create bioinert materials, but rather materials that can respond to the cellular environment around them to improve device integration and tissue regeneration. Since their discovery, β‐cyclodextrins (CDs) and, more recently, chitosan have served as prototypes for novel host compounds and catalysts. The use of CDs and chitosan as microvessels to perform chemical reactions has attracted the interest of chemists since the 1960s. This review mainly concentrates on the recent developments of organic reactions mediated by native or simply modified CDs and chitosan and in the use of the CDs as well as chitosan as the extra reaction field rather than the enzyme model in aqueous and alternative media as well as the recent use of the materials as bioactive restorative materials in dentistry, highlighting the enormous potential of such materials in biomedical applications and health sciences in general.