Azobenzene is one of the most extensively researched multifunctional chromophores and azobenzene including materials has a wide variety of applications due to their photoisomerization behavior. In this study, electroactive and light-harvesting carbazole and photoresponsive azobenzene units have been combined with a special macromolecular design. In this design the azo groups can be effectively isomerized in solid state, and free-standing films can be obtained by the electrochemical method. Thermal characterizations of both monomer and polymer have been performed and isomerization kinetics and solar-thermal properties have been investigated. The half-life at 60 °C and the gravimetric energy storage density of polymer was calculated as 103 min and 179.9 j g−1, respectively. Cross-linked polycarbazole structure causes dramatically increased solar thermal storage and half-life compared to respective monomer and brought unexpected mechanical and solvatochromic properties. © 2024 Elsevier B.V.