Although catalytic methods have the inherent advantage of being principally more economic than auxiliary approaches, the latter are still important tools in organic synthesis. Numerous chiral auxiliaries have been developed in the past and many of them are based on natural products or their close derivatives such as amino acids, amino alcohols, hydroxy acids, and carbohydrates. This chapter will focus on auxiliaries directly derived from amino acids and some very close derivatives such as amides and esters. Many of these auxiliaries have proven to be particularly valuable to organic chemists due to their availability, the low price, and the robustness of related methods. The chapter summarizes well-established auxiliary methods and highlights several improvements as well as a number of new approaches that have been developed within the past years.