Hybrid borate glasses containing a series of Al(III)Porphyrins were prepared by rapid melt quench technique at 230 degrees C. The hybrid glass samples were characterized by X-ray diffraction, optical absorption, steady state and time resolved fluorescence emission. Upon exposure to UV light at 260 nm, the glass samples exhibit strong blue emission and red emission at 365 nm. The appearance of large stokes shift (Delta u) and enhanced S(2) -> 50 emission at similar to 495 nm indicates that structure of Al(III)Porphyrins were inherently modified in glass matrix. Time resolved fluorescence of the hybrid glasses shows three exponential decay with tau(1) = 0.11-0.59 ns, tau(2) = 3.13-3.95 ns and tau(3) = 8.13-9.56 ns. In the present study, we investigate the influence of glassy environment on the photophysical properties and the structure of Al(III)Porphyrins in borate glass was modeled through DFT calculations. (C) 2011 Elsevier B.V. All rights reserved.