Abstract1,3‐Bis(4‐alkyloxyphenyl)‐3H‐imidazol‐1‐ium trifluoromethanesulfonates, alkyl = CH3(CH2)n–1, n = 8, 10, 12, 14 and 16, can be derived from the analogous 4‐alkyloxyphenylamines. These imidazolium salts exhibit a lamellar liquid‐crystal mesophase between 99 °C and 191 °C. The smectic‐A phase was fully characterised by polarising optical microscopy, differential scanning calorimetry and X‐ray diffraction. We report also the synthesis, lamellar crystal structure and catalytic activity of the PdII complex of the (deprotonated) carbene form of one of these salts. In addition, we measured the charged carrier mobilities in the mesophase.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)