The invention relates to an organic-inorganic composite material doped with two azo dyes as well as a preparation method and application thereof. The preparation method comprises the following steps: mixing gamma-(2,3 epoxy propoxy) propyl trimethoxy silane, ethanol and water, and further adding an acid catalyst so as to obtain a solution A; uniformly mixing tetra-n-butyl titanate and acetylacetone so as to obtain a solution B; uniformly mixing the solution A with the solution B so as to obtain organic-inorganic composite matrix mother liquor; putting 4-hydroxyazobenzene and disperse red 1 into the organic-inorganic composite matrix mother liquor, and uniformly stirring so as to obtain a turbid liquid; and depositing the turbid liquid onto a glass slide by using a spinning coating process so as to form a film, and performing thermal treatment on the film, thereby obtaining the organic-inorganic composite material doped with two azo dyes. By adopting an improved sol-gel technique, and with the combination of the spinning coating technique, two azo dyes are doped together, and a prepared material has a function of simultaneously treating double input optical signals under the stimulation of two beams of pump light of different wavelengths.