The formation of self-assembled dialkyl disulfide-functionalized monolayers containing diacetylenes is reported for the first time. The diacetylene derivative used was [S(CH2)(2)COO(CH2)(9)C drop CC drop C(CH2)(13)CH3](2) and was seen to form well-ordered monolayers when adsorbed on gold from THF. The monomer was readily converted to the polymeric form by a short exposure to UV radiation. A "blue" polymer was formed which was stable against further irradiation; that is, it did not become "red". During the polymerization the alkyl side chains displayed some reorganization.