The synthesis and the optical properties of the novel aryleneethynylenes (7, 8) and arylenebutadiynylenes (10, 11) using either a Heck-type or a Hay-type coupling are reported. The route reported here also makes meta-linked arylene-alkynylenes accessible. The number-average degree of polymerization of the obtained polymers is between 13 and 60. Some of the materials show promising optical properties (photoluminescence).