Sol-gel processing has been used to make optically transparent gel-silica matrices that have interconnected porosity in the 12 to 14 A scale. Optically active organics have been impregnated into the porous matrices resulting in optical composites with unique properties. However, for certain organic phases, such as required for solid state dye lasers or in-situ photo-polymerization, matrices with a large pore diameter and larger volume fraction of porosity are required. A new processing method that controls aging of gel-silica monoliths in an alkaline NH4OH environment followed by drying and stabilization from 600-1150°C results in optically transparent gel-silica matrices. The surface areas of the matrices range from 770 to 200 m2/g with total pore volumes from 0.5to 1.15 cm3/g, and mean pore radii from 20 A to 135 A. Very narrow pore size distributions are achieved and the pore configuration can be changed from ink bottle to a cylindrical cross section. Optical applications of matrices with these new textures are described, including performance of a solid state dye laser made by impregnating large pore gel-silica matrices (90 A average radius pores and 1.0 cm3/g pore volume) with 4 PyPO-MePTS lasing dye.