Herein, we report synthesis and manipulation of new reinforced polyamide nanocomposites filled by modified ternary (Mg, Zn, Al) layered double hydroxide by a solution intercalation technique. First, a new optically and electrochemically active polyamide 5 containing a new combination of azobenzene unit, imine function, triphenylamine segment and pyridine moiety in the main chain was prepared by reaction of a newly dicarboxylic acid 3 and 2,6-diaminopyridine 4. Then, two resulting nanocomposites containing 3 and 6% of DLDH were prepared and structures, morphology, electrochemical activity, thermal and optically properties of them were investigated. Also, dye-modified ternary layered double hydroxide was obtained by a co-precipitation method. The π–π* transition related to trans azobenzene chromosphere showed a single absorption between 290 and 350 nm. The electrochemically active behavior of resulting films onto glassy carbon exhibited cyclic voltammetry peak at 0.5–0.9 V, which was enhanced by filling polymer matrix with modified DLDH. On the other hand, significant improvements at T5, T10 and char yields of resulting nanocomposites were observed as compared to the polymer.