Preparation of two symmetrically substituted tetrayne monomers has been described which have directly Linked heteroaryl moieties (2-thienyl and 3-quinolyl) as the side groups. These two monomers undergo solid state polymerization when heated. The polymerization rate is directly related to the heating rate. The polymers are insoluble in organic solvents. The polymerization seems to proceed in two steps to yield polymers with irregular structure but with aromatic character. The polymers have been characterized by spectroscopic techniques, such as FTIR and solid state C-13 NMR spectroscopy, and by powder XRD. One of the monomers could be obtained in single-crystal form, whose X-ray structure revealed the arrangement of the molecules in the crystal lattice in context with the topochemical reaction.