Lead phthalocyanine (PbPc) was first successfully doped in organic-inorganic matrix by choosing proper alkoxy-silane containing amino-group by sol-gel processing. The characteristics of PbPc in sol and gel were studied using optical absorption spectroscopy. The results show that the presence of PbPc monomer in the sol and gel is strongly controlled by the pH value of sol, and the action of amino-group is an important factor for PbPc monomer able to exist in gel.