Nanocrystalline (<100 nm) red emitting Eu3+- doped M3Al2O6 (M = Ba, Ca and Sr) phosphors were prepared by an aqueous sucrose-PVA-metal ion complex route. The aqueous sucrose-PVA solution includes 20 mol% PVA, and the method is based on the dehydration of a transparent metal ion-sucrose-PVA solution to a highly viscous liquid and then precursor formation by heating at 250°C. The phase formation and the crystallite size measurements were made by x-ray diffraction techniques. Photon correlation analysis revealed that all synthesized phosphor particles range in size from 400 nm to a few microns. The photoluminescence (PL) and PL excitation characteristics have been investigated. All samples have broad CT bands centered at around 269 nm and only the Ca3Al2O6:Eu3+ exhibited the characteristic f-f transitions of Eu3+ ions mainly located at 396 and 465 nm in comparable levels with the CT band. The emission spectrum of Ca3Al2O6:Eu3+ is dominated by the red (5D0 ¡æ 7F2) transition band located at 614 nm, however the Eu3+ doped Sr3Al2O6 and Ba3Al2O6 phosphors have comparable emission intensity in the red (5D0 ¡æ 7F2 ) and orange (5D0 ¡æ 7F1 ) transition bands. The highest intensity of the red emission was obtained when the Ca3Al2O6:Eu3+ phosphor was excited at 396 nm.