Homogeneous monolith of AlPO4 gel doped with Rhodamine 6G (Rh6G) in different dye concentration is prepared by one step process with sol-gel method using the precursors Al(lact)(3) and H3PO4. The optical properties of AlPO4 gel doped with Rh6G have been characterized by UV-vis absorption spectra and fluorescence spectra. Rh6G molecular J-dimers and H-dimers even multimers are analyzed by excitation spectra based on Exciton theory. The structure of AlPO4 gel doped with Rh6G is investigated by Al-27 and P-31 Magic Angle Solid Nuclear Magnetic Resonance (MAS NMR), Al-27 {P-31} Rotational Echo Double Resonance (REDOR) NMR and Al-27 Triple Quantum Magic Angle Spinning (TQ-MAS) NMR. Based on the results of optical spectra and the structural analysis by NMR techniques, The AlPO4 gel doped with Rh6G dye with molar ratio of Rh6G/Al(lact)(3) of 1 x 10(-4) displays excellent optical properties. (c) 2010 Elsevier B.V. All rights reserved.