A representative number of bench-stable nonsymmetric diarylcarbenium tetrafluoroborates have been isolated via the direct coupling of aryl (or heteroaryl) aldehydes and N-heteroarenes and fully characterized. They have proven to be highly stable in the presence of both EDG and EWG substituents. An (E)-iminium vinylogous substructure has been shown as the common cation scaffold by X-ray analysis and by NOE determination.