In this work, we present a comprehensive investigation of triarylpropargyl cations with electronic stabilization and steric protection, which were readily prepared by treatment of the corresponding triarylpropargyl alcohols with acid. Their structural parameters and electronic properties were examined by X-ray diffraction and IR and UV/Vis spectroscopy. In the crystal, the ion pair of the triarylpropargyl cation 2 + and common anions forms consistently charge-segregated assemblies for a series of small counter anions, and a subtle change in the packing arrangement causes a drastic change in solid-state absorption due to the different effectiveness of π-π interaction in a crystal.