The dissimilarities and features of the crystal structure of ZnAl LDH-NO3 conversion layers grown directly on pure zinc and aluminum alloy 2024 were investigated in the present paper. Although the nature of the cations in the double hydroxides are the same in both cases (Al3+ and Zn2+), their sources differ according to the substrate. This leads to a difference in the cationic layers and interlayer structure, which consequently influences the anionic exchange reaction. In the frame of this work, the kinetics of the anion-exchange of nitrate by chloride was investigated as well as the crystal structure of the resulting ZnAl LDH-Cl on both substrates. Synchrotron high-resolution X-ray diffraction was the main method to obtain structural information and was supported by additional calculations and scanning electron microscopy. The current study revealed noticeable changes on the positioning of the interlayer atoms for the ZnAl-LDH-Cl on zinc in comparison with the ones on AA2024 substrate.