Metallophthalocyanines　(MPc)　have　excellent　photoelectricity　properties.　However,　their　low　solubility　in　the　sol-gel　precursor　and　their　tendency　to　aggregate　make　it　difficult　to　get　their　homogeneous　composites　with　the　traditional　sol-gel　schedule.　To　overcome　this　problem,　a　newly　developed　＇in　situ　synthesis＇　technique　during　the　sol-gel　process　was　successfully　used　to　synthesize　transitional　metallophthalocyanines　in　the　silica　xerogel　matrix.　As　a　result,　a　new　kind　of　organic/inorganic　nanocomposite　was　obtained.　The　characterizations　of　the　glass　sample　and　the　extract　were　carried　out　by　methods　of　IR,　UV/Vis　and　fluorescence　spectra.　The　microenvironment　of　MPc　is　inferred　from　the　change　of　the　pore　structure　of　the　matrix,　and　the　reason　why　MPc　exist　in　the　form　of　a　monomer　is　given.　From　the　view　of　the　different　structures　of　transitional　metallophthalocyanines　and　rare-earth　metallophthalocyanines,　it　is　also　discussed　why　rare-earth　metallophthalocyanines　cannot　be　synthesized　in　the　matrix　while　transitional　metallophthalocyanines　can.　©　2002　Elsevier　Science　B.V.　All　rights　reserved.