Azobenzene macrocycles (AzMs) represent a class of azobenzene that are typically photoswitchable with good switching yields of E and Z isomers at certain photostationary states. Here, the synthesis and versatile functionalization of 12-membered AzMs is presented to obtain various meta- and para-aryl-substituted AzMs in high yields of 71-98%. At different positions in the periphery, these substituents significantly impact on the thermal half-lives of the less-stable Z isomers. Para-substitution leads to faster thermal relaxation than meta-substitution, and electron-donating groups lead to a faster relaxation than electron-withdrawing groups.