In the present work, composites of poly(methyl methacrylate)/alkali rare earth aluminate photoluminescent pigment (PMMA/AREAPP) (100/0, 98/ 2, 96/4, 94/6, and 92/8 wt/wt%) were prepared using mixture technique. The pigment has the composition formula ofMeO.xAl2O3.ySiO2:Eu (Me = Ca,Mg, Sr, Ba, x = 0.5-2.0, y = 0.005-0.5) which is activated by rare earth element (Eu). The reflectance spectra and the tristimulus values aswell as the color parameters were employed to characterize and reveal the miscibility map and the relationship of the structure properties. The study has been extended to include the absorption and extension coefficients of the prepared composites, the band tail width and band gap energies for the composites. From the obtained results, it is found that the organic parts are attached with the inorganic parts in the PMMA/AREAPP composites.Also, it is clear that theAREAPP powder has a great effect on improving the performance properties of PMMA and greatly depends on its concentration in the composite.