The ion exchange of the luminescent probe 1-pyrenemethylamine (PYMA) into zirconium phosphate (ZrP) layered materials has been accomplished. The matrices used were the hexahydrated 10.3 Angstrom phase of ZrP (10.3 Angstrom ZrP, where 10.3 Angstrom represents the interlayer distance) and butylammonium-exchanged ZrP (BAZrP) with an expanded 18.6 Angstrom interlayer distance. The XRPD patterns for the 10.3 Angstrom ZrP after PYMA exchange (PYMA-exchanged ZrP), at high PYMA concentrations, show an increase in the interlayer distance from 10.3 Angstrom in unexchanged 10.3 Angstrom ZrP to 23.5 Angstrom in PYMA-exchanged ZrP, indicating PYMA intercalation. The luminescence spectrum for the PYMA-exchanged ZrP exhibits an excimer band at 458 nm that is absent in the luminescence spectrum of PYMA in aqueous solution at low concentrations. The intensity of the excimer emission increased at low PYMA concentrations. These results are in contrast to experiments using the BAZrP matrix. The XRPD patterns for PYMA-exchanged BAZrP do not show changes in the interlayer distance, which suggests that PYMA is not being intercalated and is only surface bound. The luminescence spectrum for PYMA-exchanged BAZrP exhibits a lower emission intensity in its excimer band, at different PYMA concentrations, compared with the PYMA-exchanged ZrP excimer band. For PYMA-exchanged ZrP, we propose a process in which exchange at low PYMA concentrations occurs at external surface sites with clustering promoting excimer formation followed by exchange at high PYMA concentrations occurring at interior sites reducing excimer formation.