Three symmetrical diacetylenes (DAs) bearing tetraalkylammonium substituents have been prepared, namely 1,6-bis(triethylammonium)hexa-2,4-diyne diiodide (2), dinitrate (3), and bis[bis(trifluoromethylsulfonyl)imide] (4). For these three salts, the duality between polymerization and carbonization has been investigated, and the results have been rationalized in terms of solid-state organization and molecular structure. These DAs have been irradiated at 254 nm with concomitant annealing at 80 °C (4) or 110 °C (2 and 3), and the lack of polydiacetylene (PDA) formation agrees with the fact that the C≡C-C≡C rods do not have a suitable orientation for 1,4-addition. Compound 4 is an ionic liquid. This DA starts melting at 88 °C with a maximum peak value of 104 °C, as ascertained by differential scanning calorimetry (DSC) and thermogravimetric (TG) analyses. It is stable in the liquid state at 120 °C for several hours and remains unchanged at 170 °C for a few minutes without any sign of PDA formation, which means that if some kind of organization exists in the liquid phase, it is not helpful for 1,4-polymerization. Thermolyses of 2-4 have been conducted under a nitrogen flow up to 220 °C (3) and 1200 °C (2 and 4). In all three cases, graphite-like carbon materials were obtained. The graphite-like structures start to form around 200 °C, that is the temperature where cycloaromatization of the triple bonds takes place. The residues from the pyrolyses of 2 and 4 exhibit nitrogen contents of 1.75 and 1.40 wt%, respectively, and powder X-ray diffraction and Raman analyses indicate that these materials have coherently scattering domain sizes in the range 1-3 nm depending on the crystallographic direction. The BET specific surface area of 2@1200 derived from dinitrogen sorption experiments is 88 m2 g1 and that of 4@1200 33 m2 g1. These values are much higher than those measured in previous work for carbon residues prepared at 1100 °C from imidazolium- and benzimidazolium-appended diacetylenes, thereby highlighting the pivotal influence of the size of the cation on the microstructure of the resulting carbon material. In addition, 2@1200 appears to be mostly microporous and 4@1200 mesoporous, which suggests that the anion also plays a central part in the structuring of the final solid. Last, X-ray Photoelectron Spectroscopy (XPS) analysis of 4@1200 indicates that, besides nitrogen, this residue also contains small amounts of fluorine and sulfur, thus making carbonization of ionic diacetylenes an alternative method to introduce doping elements in a graphite structure.