Efficient syntheses of all five possible isocyanoazulenes, the four isomeric archetypal compounds CN1Az, CN2Az, CN4Az, and CN6Az, as well as the 1,3-di-tert-butyl derivative of CN5Az (Az = azulenyl), are described. Compounds CN1Az and CN2Az show unexpected shifts of the S0 → S1 transition in their electronic spectra relative to azulene. The origins of these “anomalous” shifts have been addressed by DFT calculations, cyclic voltammetry, and comparison of the electronic spectra of isocyanoazulenes with those of the corresponding isomeric cyanoazulenes. Despite the high propensity of the azulenic nucleus to undergo multihapto coordination and C−C coupling in the presence of low-valent metals, the isocyanoazulenes react with 1/6 equiv of Cr(η6-naphthalene)2 to afford thermally stable Cr(CNxAz)6 (x = 1, 2, 4, 6), which contain six discrete azulenyl groups separated from the Cr center by isocyanide linkers. All Cr(CNxAz)6 species undergo oxidation to form the corresponding paramagnetic cations [Cr(CNxAz)6]+, which have been crystallographically characterized. Changing the atom of attachment of the azulenyl groups to the “Cr(CN)6” core substantially alters the donor/acceptor properties of the isocyanoazulene ligands. The half-wave Cr0/+ and Cr+/2+ redox potentials for [Cr(CNxAz)6]z form the “electrochemical series” that constitutes a quantitative measure of electronic inhomogeneity of the azulenic framework. Unpaired spin delocalization within the azulenic moieties of [Cr(CNxAz)6]+ has been observed by multinuclear NMR. The CrI(dπ)→CNxAz(pπ*) interaction has been shown to be an important contributor to the mechanism of unpaired electron delocalization in [Cr(CNxAz)6]+.