Hydrotalcite-like compound containing metal cations such as Mg2+, Al3+ and Ni2+ was characterized using Ni K-edge EXAFS and in situ Ni K-edge XANES techniques for clarifying its bonding environment around Ni2+ sites and structure changes during calcination from room temperature to 550 °C, respectively. At the fixed molar ratio of Mg/Ni/Al of 2/1/1, the results obtained from EXAFS analysis showed a slight blue shift before and after the calcination at 550 °C and a reduction in white line peak; the best fits of the two samples revealed tiny change in coordination number about 7 for Ni-O path but considerable difference for Ni-Mg(Al) path from about 4.5 to 9.5, confirming a modification from brucite like to mixed oxide structure. On the other hand, bond distances of the Ni-O and Ni-Mg paths nearly fixed at about 2.06 Å to 3.0 Å reflected stability of the cationic bond order on each plane, but partial collapse and decomposition of the interlayer formed by water molecules and anion CO3 2- after the calcination. Linear combination fit extracted from the in situ Ni K-edge XANES also confirmed the changes along with the calcination such as slow and fast decreases of brucite fraction at 150 °C and 330 °C, respectively, in corresponding to the mixed oxide fraction increases. The achieved bonding structures were also applied to explain acid-base occurrence of the hydrotalcite-like material, especially the acid sites generated by different static charges along with the bonds. The explanation was illustrated by NH3-TPD method.