We　report　here　the　preparation　of　nickle　tetrasulfo-phthalocyanine　(NiTSPc)-doped　silica　xerogel　matrix　obtained　by　sol-gel　technique.　The　evolution　of　silica　matrix＇s　texture　and　the　rate　during　the　sol-gel　process,　as　well　as　silica　xerogel＇s　pore　structure　were　studied.　Dimerization　behavior　of　NiTSPc　molecules　was　characterized　by　electronic　absorption　spectra,　and　changes　in　the　absorption　spectra　were　correlated　with　various　stages　of　the　sol-gel　process.　The　results　show　that　in　the　composites　NiTSPc　concurs　in　the　forms　of　monomer　and　dimer,　and　dimerization　is　stronger　during　the　latter　stages.　The　reason　is　given　from　the　change　in　the　micro-environment　in　which　NiTSPc　existed　during　the　sol-gel　process.