Pd-catalyzed direct C2 arylation and Cu-catalyzed direct one-pot alkynylation/intramolecular cyclization of azolium N-imides are reported. Various acetylenes, aryl iodides, and 1-alkyl substituents were examined. The mild protocol allows direct C2 arylation of azolium N-imides without the use of specialized reagents together with novel one-pot regioselective preparations of imidazole-pyrazolo and pyrazolo-1,2,4-triazole ring systems. The electronic properties of selected examples were examined by fluorescence spectroscopy.