Abstract: Hydrotalcite-like compounds (HT) with 24%–48% Al3+-substitution have been synthesized in the Mg2+-Al3+-Fe(CN)64- system. Conditioning of the synthesized and air-dried compound with K4Fe(CN)64- solution at 80°C was essential to obtain the 80%–90% pure ionic Fe(CN)64- form on an equivalent basis. A linear decrease in ao with an increase in the mole ratio of R = Al3+/(Mg2+ + Al3+) was extended to R = 0.48. The formation of highly Al3+-substituted HTs has been corroborated by the decrease in the hexagonal lattice constant ao down to 3.016 Å. The ao value was independent of the interlayer anions. The CO2 adsorption profiles were dependent upon both the Al3+-substitution and the interlayer distance. The isosteric heat of CO2 adsorption was 43.3 kJ mol-1 in the range of adsorption of 20 to 40 cm3 g-1 at 298 K and 0.1 MPa.