Alanyl-alanine-derived poly(isocyanide)s possess a helical structure that persists even in aqueous media. These rigid macromolecules possess a regular distribution of carboxylic acid-terminated side chains which for the first time allows the study of the templating process involved in biomineralization using a shape-persistent polymeric template. It is demonstrated that in the case where the polymer derived from l-Ala-d-Ala is used the formation of apple core-type calcite crystals is controlled both by nucleation of the (01.1) face and subsequent adsorption of the polymer to the {hk.0} faces of the growing crystal. A small change in the secondary structure of the template that is introduced by using the polymer derived from l-Ala-l-Ala is directly reflected in the lower degree of control over the crystallization process.