The first two α‐sila‐dipeptides, 7 and cyclo‐sila‐dipeptide 8, were synthesized and characterized by several methods, including X‐ray crystallography. Bulky t‐BuMe2Si substituents provide some kinetic stabilization to the synthesized molecules. 7 and 8 are the first examples of a “Si for C switch” in the central α‐position of an amino acid or a peptide, in which silicon is bonded to both the amino and the carbonyl groups. Two α‐sila‐dipeptides: The acyclic 1 and the cyclic 2 were synthesized, isolated and characterized by X‐ray crystallography. 1 and 2 are the first examples of a “Si for C switch” at the central α‐position of amino acids and peptides, enriching the library of acyclic‐ and cyclic‐dipeptides (diketopiperazines), including biologically active compounds.