The intercalation of polyamine into α-zirconium phosphate (α-ZrP) was examined at room temperature and 80 °C. In triethylenetetramine (3E4A), tetraethylenepentamine (4E5A), and pentaethylenehexamine (5E6A) the temperature of the reactions influenced the rate of intercalation, but did not effect the structure of the intercalation compound. On the other hand, the ratios of the constituent phases in the N,N′-bis(3-aminopropyl)-1,3-propanediamine (3P4A) intercalated solid were greatly influenced by the reaction temperature, and two phases with the different interlayer distances could be formed by controlling it. In the phase with an interlayer distance of d = 20 Å, obtained predominantly at 80 °C, 3P4A was present as a monolayer of extended molecules in the interlayer region, in which the longitudinal axis of 3P4A was inclined at ca. 60° to the α-ZrP layers. In the phase with d = 17 Å, obtained at room temperature, 3P4A existed as a bent form. These polyamine intercalated solids drastically adsorbed acetic acid, formaldehyde, acetaldehyde, and cinnamaldehyde.