Freebase tetra phenyl porphyrin (H2TPP) and its derivatives in different concentration ranges (0.5-2.0 mg per 12 g of boric acid) were incorporated into borate glass matrix by melt quenching technique at 230 degrees C. The formed glasses were stable and in green colour. The optical absorption and emission properties are different from that observed in solutions. The absorption spectrum shows a two line pattern Soret band at 435-454 nm and Q-band at 665-701 nm. The emission spectrum shows strong S-2 -> S-0 emission at 490-520 nm region and S-1 -> S-0 emission at 725-810 nm. The time resolved fluorescence decay of S-1 -> S-0 emission shows three exponential decay. For example, in the case of 2 mg of H2THP doped glass the lifetimes were found to be tau(1) = 0.511 ns (26.7%), tau(2) = 10 ps (64.68%) and tau(3) = 3.965 ns (8.62%). These unusual photophysical properties were found to arise from different structural motifs of porphyrin in the glass. These structures were further modeled through reactions of porphyrin with BF3O(C2H5) in solution and DFT calculations. (C) 2010 Elsevier B.V. All rights reserved.