Novel polyazomethines containing triphenylamine structure in the main chain. have been prepared on a way of polycondensation of 4,4'-diformyltriphenylamine with aromatic diamines in HMPT solution with the goal to study interactions between polymer chain (Ps) and dopant (methanesulfonic acid: MSA, m-cresol: MC and p-chlorophenol: pClp) by FTIR, UV-vis and PL measurements. The electronic absorption spectra and photoluminescence spectra of polyazomethines detected in various solutions were dependent on the diamines structures and could be tuned by supramolecular modification via protonation or H-bond formation, of imine group with the dopant. Preliminary results suggest that the polyazomethines can be blue light emitting materials.