Incorporatingdiversecomponentsintometal-organic frameworks (MOFs) can expand their scope of properties and applications.Stratified MOFs (sMOFs) consist of compositionally unique concentric domains (strata), offering unprecedentedcomplexity through partitioning of structural and functional components. However, the labile nature ofmetal-ligand coordination handicapsachieving compositionally-distinct domainsdue toligand exchange reactions occurring concurrentlywithsecondary strata growth. To achieve complex sMOF compositions, characterizingand controllingthe competing processes of new strata growth and ligand exchangeare vital. This work systematicallyexaminescontrolling ligand exchangein UiO-67 sMOFs by tuning ligandsterics. We present quantitative methodsfor assessing and visualizing the outcomes of strata growth and ligand exchange that relyon high-angle annular dark-field images and elemental mapping via scanning transmission electron microscopy-energy dispersive X-ray spectroscopy. In addition, weleverageligand stericsto create 'blocking layers'that minimizeligand exchange between strata which are particularly susceptible to ligand exchange and inter-strata ligand mixing. Finally,we evaluatestrata compositional integrity in various solvents and find that sMOFs can maintain their compositions for >12 months in some cases.Collectively, these studies and methodsenhanceunderstanding and control overligandplacement in multi-domain MOFs,factors that underscore careful tunning of properties and function.