The kinetics of the thermal cis-trans isomerization was determined in a series of crown ethers containing the azobenzene moiety incorporated into the crowns of various sizes (10- to 19-membered crowns), dissolved in liquid isooctane and in polymer matrixes (PMMA and polystyrene). The kinetic parameters (activation energies and pre-exponential factors) were determined from temporal evolution of the absorbance measured at one of the maxima due to the pi-pi* transition of the trans forms of the molecules, using both isothermal and nonisothermal procedures. Molecular structures and electronic spectra of both trans and cis forms were calculated employing an ab initio method with 3-21G* basis set and semiempirical ZINDO-S, respectively. A comparison of the quantum-chemical calculations with the experimental results shows that one may exclude the splitting of the UV absorption bands of the trans forms of the molecules under study that resulted from a coexistence of several conformations of these molecules. A linear relationship was found between the activation energy and logarithm of the pre-exponential factor of the thermally driven cis-trans isomerization: ail molecules follow a common dependence, except for the smallest (10-membered) crown ether.