Using 4-mercaptomethyl-3, 6-dithio-1,8-octyl dithiol and divinylbenzene as raw materials and 2-hydroxy-2-methylphenylacetone as photoinitiator, the results showed that the polymers had excellent optical properties. Among them, when the functional group molar ratio of thiol to double bond was 3:5, the polymer film transmittance was 94%, and the refractive index reached 1.613. In terms of adhesive application, the cured polymer achieved an adhesive strength of 0.9 MPa on polar glass, and thus it can be considered for use as an optical adhesive. In addition, the monomer blends exhibited excellent normal temperature and high temperature storage stability within 30 days.