Although metal-phenolic species have emerged as one of the versatile material-independent-coating materials, providing attractive tools for interface engineering, mechanistic understanding of their film formation and growth still remains largely unexplored. Especially, the anions have been overlooked despite their high concentration in the coating solution. Considering that the anions are critical in the reactivity of metal-organic complex and the formation and/or property of functional materials, we investigated the anionic effects on the characteristics of film formation, such as film thickness and properties, in the Fe3+-tannic acid coating. We found that the film characteristics were strongly dictated by the counteranions (e.g., SO42-, Cl-, and Br-) of the Fe3+ ion. Specifically, the film thickness and properties (i.e., mechanical modulus, permeability, and stability) followed the reversed anionic Hofmeister series (Br- > Cl- > SO42-). Mechanistic studies suggested that more chaotropic anions, such as Br-, might induce a more widely extended structure of the Fe3+-TA complexes in the coating solution, leading to thicker, harder, but more porous films. The reversed anionic Hofmeister effect was further confirmed by the additive effects of various sodium salts (NaF, NaCl, NaBr, and NaClO4).