The 1,10-phenanthrolinium cation is introduced as a new building block for the design of ionic liquid crystals. 1,10-Phenanthroline, 5-methyl-1,10-phenanthroline, 5-chloro-1,10-phenanthroline, and 4,7-diphenyl-1,10-phenanthroline were quaternized by reaction with 1,3-dibromopropane or 1,2-dibromoethane. The resulting cations were combined with dodecyl sulfate or dioctyl sulfosuccinate anions. The influence of both the cation and anion type on the thermal behavior was investigated. Several of the complexes exhibit mesomorphic behavior, with smectic E phases for the dodecyl sulfate salts and smectic A phases for the dioctyl sulfosuccinate salts. Structural models for the packing of the 1,10-phenanthrolinium and anionic moieties in the liquid-crystalline phases are presented. The ionic compounds show fluorescence in the solid state and in solution.