Humans have intentionally used biological materials such as bone, ivory and shells since prehistoric times due to their particular physical and chemical properties. The composite nature of biological materials at the nanoscale combined with an important structural hierarchy up to the macroscopic level is responsible for these exceptional properties. In this chapter we discuss the relation of the structural features of different biological materials within their archaeological and historical contexts along with their anthropological use and function. Amid the wealth of biological materials of archaeological interest, a special attention is paid to carbonate-based materials such as corals and shells and phosphate-based ones, including bone, teeth, ivory and antler. The structural features of these archaeobiominerals at different length scales down to the nanoscopic scale are highlighted in this chapter as they allow drawing conclusions on ancient working techniques, the provision and circulation of raw materials, anthropological heat processes, and, last but not least, on diagenetic changes and authentication purposes. The informative potential of observations of archaeological biological materials at different length scales is finally illustrated by some study cases.