A series of doubly cyclopalladated complexes of azobenzene and its unsymmetrical substituted derivatives, namely, {LPdCl(mu-AZB)LPdCl}, where AZB is azobenzene, 4-methylazobenzene, 4-aminoazobenzene, or 4-(dimethylamino)-4'-nitroazobenzene, while L is N,N-dimethylformamide, dimethylsulfoxide, or pyridine, have been prepared. Their structural and spectroscopic properties were determined by X-ray diffraction analysis as well as by H-1 NMR, IR, UV-vis, and fluorimetric studies. Experimental results were rationalized by quantum chemical calculations. Crystal structures of several complexes have been resolved, and for the first time, it was demonstrated that the cyclopalladation may take place at the azobenzene aromatic ring having the strong electron-withdrawing substituent at the para position. In all cases, the metalated carbon and N,N-dimethylformamide or dimethylsulfoxide ligands are mutually trans, whereas the pyridine ligands are in the cis arrangement. cis/trans isomerism in the isolated compounds is explained by comparing the calculated energies of isomeric structures. All of the complexes absorb strongly in the visible region, and according to time-dependent density functional theory calculations, most of the absorptions can be attributed to intraligand pi ->pi* or metal-to-ligand charge-transfer transitions. The fluorescence emission was observed for the complexes with 4-aminoazobenzene or 4-(dimethylamino)-4'-nitroazobenzene. The aromaticity of palladacycles is evaluated by several aromaticity indices and related to relevant experimental findings.