A 2, 4, 6-Tris (4-nitrophenyl) pyridine (TNPP) was synthesized from nitrobenzaldehyde and nitroacetophenone in glacial acetic acid and conformed. The TNPP monomer further reacted with diamines such as benzidine (TNPP-B) and phenylenediamine (TNPP-P) to obtain azo linked polymers for photochemical activity. These polymer structures were identified using different characterization techniques like FTIR, UV-visible spectroscopy, scanning electron microscope (SEM), fluorescence spectroscopy, cyclic voltammetry, DSC and TGA. The FTIR spectra of all the azo-linked functional group of polymers were observed at 1592 cm-1 and 1596 cm-1. The TNPP-B based TNPP polymer exhibit high thermal decomposition temperature (Td) at 403 °C. UV/vis absorption spectra for TNPP-B and TNPP-P were absorbed in the region 300-375, 285-385 and 350-400 nm. These polymer materials could be used for optical and energy applications.