NH3 temperature-programmed desorption (NH3-TPD) is frequently used for probing the nature of the active sites in CuSSZ-13 zeolite for selective catalytic reduction (SCR) of NOx. Herein, we propose interpretation of NH3-TPD results, which takes into account the temperature-induced dynamics of NH3 interaction with the active centers. It is based on a comprehensive DFT/GGA+D and first principles thermodynamic (FPT) modeling of NH3 adsorption on single Cu2+, Cu+, [CuOH]+ centers, dimeric [Cu-O-Cu]2+, [Cu-O22--Cu]2+ species, segregated CuO nanocrystals and Brønsted acid sites (BAS). Theoretical TPD profiles are compared with the experimental data measured for samples of various Si/Al ratio and distribution of Al within the zeolite framework. Cu reduction, its relocation, followed by intrazeolite olation processes, which are concomitant with NH3 desorption, were revealed by EPR and IR. DFT/FPT results show that the peaks in the desorption profiles cannot be assigned univocally to the particular Cu and BAS centers, since the observed low-, medium- and high-temperature desorption bands have contributions coming from several species, which dynamically change their speciation and redox states during NH3-TPD experiment. Thus, the rigorous interpretation of the NH3-TPD profiles of CuSSZ-13 in terms of the strength and concentration of the active centers of a particular type is problematic. Nonetheless, useful connections for molecular interpretation of TPD profiles can be established between the individual component peaks and the corresponding ensembles of the adsorption centers.