Here, π-conjugated planar molecules are potential candidates for applications such as semi-conductors and ferroelectric materials. The arrangement of π-systems in their assemblies is crucial for controlling their electronic properties in the solid state. In ionic π-molecules, there are two classes of assembling modes, "chargeby-charge assemblies", where anions and cations are stacked alternately, and "charge segregated assemblies", where each charged species is stacked separately. Among them, the construction of charge-segregated assemblies, which would possess semi-conductive properties, is still challenging since the proximity of ionic molecules with the same charge leads to large electrostatic repulsion. Thus, guidelines for establishing chargesegregated assemblies are still elusive, and reliable building blocks have been sought. Based on the above background, we shifted our focus to crystal structures of triarylpropargyl cations. In the crystal of 1 + TfO -(including two crystallographically independent molecules, orthorhombic, Pna21, Z=8), mol.1 and mol.2 dovetailed each other to form a ribbon-like structure. The ribbons partially overlap with the shortest C•••C contact of 3.442 (7) Å and the counter anions are positioned between them, resulting in the intermediary packing of charge-by-charge and charge-segregated assemblies. On the other hand, in the crystal packing of 2 + TfO -(monoclinic, Cc, Z=4), 2 + forms brick layer stacking with the shortest C•••C contact of 3.386(6) Å, as the completely planar shape of 2 + does not hinder the proximity of the cations. Counter anions are situated on both sides of the cationic layer, leading to charge-segregated assemblies.