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The spectral-luminescent, photochemical and lasing characteristics of some laser dyes: rhodamine, phenalemine, oxazole and p-terphenyle derivatives, incorporated into solid silica matrices during sol-gel process with different composition of silica alkoxides and geometrical forms of solid samples were studied. It is shown that optical properties of thin silica gel-films (<1 μm) are doped with organic molecules have some peculiarities compared with bulk gel-matrices. The lasing of bulk matrices with dyes and traveling wave lase in some thin films under laser excitation was observed. The proton transfer from solid matrices to the proton acceptor centre of some dyes is observed at the ground and the excited states. The molecular and laser photostability of dyes in solid silica matrices was determined, is shown that it is higher compared with the photostability of ethanol solutions of the same dyes.