A series of phthalimide- and 1,12-benzoperylene-1＇,2＇-dicarboxylic imido-linked alkynes were prepared and analyzed by UV, FT-IR, optical microscopy, and differential scanning calorimetry. The possibility to convert omega-alkynes (R-(CH2)(n)-C=CH) to diacetylenic compounds (R-(CH2)(n)C=C-C=C-(CH2)(n)-R) was investigated for R = phthalimide and 1,12-benzoperylene-1＇,2＇-dicarboxylic imide with n = 1, 3, and 9. Formation of the diacetylenic compound is usually straightforward las checked by comparison with independently synthesized diacetylenes), and in some cases heat-induced polymerization of the thus-formed diacetylenes proceeds directly. For the perylene imide-linked materials with n = 1 and n = 3 1,a-polymerization occurs, while for n = 9 1,4-polymerization occurs. The 1,4-polymerization is also observed for the phthalimide-linked materials. For R = phthalimide and n = 1 this 1,4-polymerization can only be induced by further heating, while for the analogous n = 9 compound 1,4-polymerization is already induced by UV-vis irradiation at room temperature. This is related to the flexibility of the methylene spacer in the crystal.