The intercalation of three different anions derived from carboxylic acids is reported. It was shown that the intercalated anions of cholic and diphenylacetic acids form bilayers in the LDH interlamellar domain with different interactions involved in such arrangements. Each anion species showed the same interlayer arrangement for different Zn(II)/Cr(III) ratios, probably due to the intermolecular interactions that maintain the interlayer organization, independently of the available space per anion.