This review gives an account of the coordination chemistry of supramolecular azopolymer complexes. The syntheses and structures of azomonomers and their azopolymer complexes were described. Spectral techniques such as (IR, ¹H-NMR, ESR) and thermal analysis were investigated. Supramolecular architectures assembled were exhibited through weak interaction including hydrogen bonding and π–π stacking. The spectral data indicate geometry of azopolymer complexes and the orbital reduction factors. ESR spectral data provided information about their structures on the basis of Hamiltonian parameters and degree of covalency. All the azopolymer complexes are ESR active due to the presence of an unpaired electron. The force constant F_U–O(mdyn/Å) and the bond length R_U–O (Å) of the U–O bond were calculated from the IR data and related to the electronic properties of the substituents. Wilson_s method, the matrix method, Badger_s formula, and the Jones and El-Sonbati equations were used to calculate the U–O bond distances from the values of the stretching and interaction force constants. The most probable correlations between U–O force constant to U–O bond distance were satisfactorily discussed in terms of Badger_s rule, and the Jones and El-Sonbati equations. The thermal stability was investigated using thermogravimetric analysis. The results showed that the azopolymer complexes are mostly more stable than the homopolymer. The stability of the proton ligand/metal ligand constants in the monomeric and polymeric forms was studied carefully using potentiometery. Based on the thermodynamic functions, the dissociation process is nonspontaneous, endothermic and entropically unfavorable. The metal complexes that were formed exhibited spontaneous, endothermic and entropically favorable behavior.