First, we propose a formulation based on cellulose nanofibers (CNFs) as a versatile scaffold for the facile non-covalent binding of AuNRs and chosen Azo molecule (AzoGly). The resulting hybrid material exhibited stable plasmonic and photochromic properties and structural integrity in water under elevated temperatures and UV-Vis-NIR irradiation. Second, we provide new insight into the acceleration of the Z-E Azo isomerization in the dark by using, for the first time, gold nanorods in the process. Our results contribute to the discussion regarding the eT mechanism of the reaction. Third, we show the indirect modulation of AzoGly photoswitching by performing plasmonassisted Z-E isomerization (Figure ). We subjected our composite in its Z-rich photostationary state (PSSZ) to red light and NIR irradiation (650-1100 nm, continuous waves, no overlapping with the AzoGly spectral profile), thus triggering solely thermoplasmonic effect. The resulting temperature rise affected the Z-isomer's stability and modulated the Z-E isomerization kinetics. Fourth, we propose means to quantify the extent of the thermoplasmonic effect by monitoring kinetic changes in the Z-E isomerization of Azo. Hence, we present prospects for Azo molecules as molecular thermometers. Finally, through advanced statistical modelling of the kinetic data, we confirm the major contribution of the thermoplasmonic effect upon irradiation and the instantaneous, ON-OFF control it grants over Azo Z-E isomerization. Hence, we also suggest the application of the Autoregressive Integrated Moving Average (ARIMA) statistical model in the analysis of photochemical phenomena.