Azobenzenes, being T-type photochromes, exhibit temperature-dependent Z-E isomerization in the dark. We measured thermal back-isomerizations of AzoGly component at several temperatures to assess kinetic and thermodynamic differences between the stability of the Z-isomer in materials with and without Au. Samples were first irradiated with UV (to reach PSSZ), and then, their return at a specific temperature in the dark to the E-rich PSS (Figure ) was monitored by measuring changes in the extinction of the π→π * AzoGly band as a function of time. Collected data confirm the first-order kinetics of the process (Figure ). Our results indicate an increased reaction rate with increasing temperature regardless of the presence of Au (Figure ). We determined the set of kinetic and thermodynamic parameters of the ongoing reaction (Table and Figure ) by employing Arrhenius (Equation S2) and Eyring (Equation S3) equations. We observed that the activation energy of the Au-containing sample, (69.9 ± 4.2) kJ mol -1 , is about 30 kJ mol -1 lower than for the control sample without gold, (99.8 ± 12.5) kJ mol -1 (Table ). A lower activation barrier for the thermal Z-E isomerization of Azo in the presence of gold proves the catalytic role of AuNRs in the dark. This catalytic boost is also visualized on the thermal relaxation profiles. Sample with Au-2 plasmonic core reaches a plateau at the same temperature faster than composite without Au. However, the catalytic influence of nanoparticles decreases with increasing temperature (Figure ).