The E. colisiderophoreenterobactin, one of the strongest FeIII chelators known to date, is also capable of binding SiIV under physiological conditions. We report on the synthesis and structural characterization of the tris(catecholate) SiIV–enterobactin complex and its GeIV and TiIV analogues. Comparative structural analysis, supported by quantum‐chemical calculations, reveals the correlation between