The studies for this PhD thesis showed the preparation, characterization and application of new-type surface-mounted metal-organic frameworks (SURMOFs). The aims were to: (1) heteroepitaxially grow MOF-on-MOF multilayer systems with huge lattice mismatch; (2) modify azide-based SURMOFs using alkyne-azide click chemistry; (3) chemically pattern SURMOFs using postsynthetic modification (PSM); (4) engineer UHM-3 SURMOFs with quantitative Cu(I) defects using postsynthetic thermal treatment.