With the need for a precise description of the long‐range electronic effects of a perfloroalkyl chain (F‐ponytail) grafted onto metal chelators, we studied in detail the effect of a spacer inserted between the polar complexing head and the F‐ponytail, in relation to the metal coordination ability of the resulting molecules. The prepared molecules were then applied for the extraction of various metals from an aqueous phase into an organic phase, and the optimum spacer length could be estimated to be between three and four methylene units, according to the extraction conditions. The study also revealed the difficulty of modeling and anticipating the tiny energy differences involved in the extraction process and the importance in peculiar cases to go beyond only these studied inductive effects to understand better the factors that govern the stabilization of a metallic cation in a complex fluorous phase.