The key step in accessing the title species (5), the first nonbenzenoid diisocyanobiaryl, involved an unexpected homo-coupling of a 6-bromoazulene derivative. The reversible 2e(-) reduction of 5 was addressed electrochemically and computationally. The shifts in energies of the S-0 -> S-1 and S-0 -> S-2 transitions for a series of related 6,6'-biazulenyl derivatives correlate with the e(-)-donating/-withdrawing strength of their 2,2'-substituents but follow opposite trends. Species 5 adsorbs end-on (eta(1)) to the Au(111) surface via one of its -NC groups to form a 2-nm-thick film. In addition, bimetallic coordination of 5's -NC termini can be readily achieved.