Abstract. The ternary Zintl phase Ca3Ag1+xGe3–x (x = 1/3) was synthesized by the high‐temperature solid‐state technique and its crystal structure was refined from single‐crystal diffraction data. The compound Ca3Ag1.32Ge2.68(1) adopts the Sc3NiSi3 type structure, crystal data: space group C2/m, a = 10.813(1) Å, b = 4.5346(4) Å, c = 14.3391(7) Å, β = 110.05(1)° and V = 660.48(10) Å3 for Z = 4. Its structure can be interpreted as an intergrowth of fragments cut from the CaGe (CrB‐type) and the CaAg1+xGe1–x (TiNiSi‐type) structures, and it therefore represents an alkaline‐earth member of the structure series with the general formula R2+nT2X2+n with n = 4. Unlike the rare‐earth homologues that are fully ordered phases, one seventh of the atomic sites in the unit cell of the title compound are mixed occupied (roughly 2/3Ge and 1/3Ag), and this can be explained by the Zintl concept. The alloying of this phase using aluminum metal yielded the isotypic solid solution Ca3(Ag/Al)1+xGe3–x, in which the aluminum for silver substitution is strictly localized in the TiNiSi substructure, revealing the very different functionality of the two building blocks.