The synthesis of monodisperse polymers with a defined monomer sequence is a new challenge in polymer chemistry. Recently, we introduced a novel synthetic strategy towards monodisperse, sequence-defined poly(amidoamine)s based on the stepwise assembly of diamine and diacid building blocks on a solid support. Here we introduce the first chiral building block suitable for the automated poly(amidoamine) synthesis. The synthetic strategy utilizes natural amino acids as starting materials, thus providing a variety of chiral building blocks with different functionalities in the side chain. As a first chiral monomer, L-alanine is transformed into a mono Fmoc-protected diamine building block and successfully introduced into poly(amide) segments.