Well-defined　3d-4f　heterometallic　supramolecular　architectures　have　attracted　attention　because　of　their　applications　in　the　field　of　luminescence　and　magnetism.　However,　covalent　metallo-supramolecular　discrete　complexes,　decorated　with　hetero-metallic　vertices,　have　never　been　reported　because　of　the　difficulties　in　design　and　control.　Herein,　we　report　a　series　of　covalent　metallo-supramolecular　discrete　complexes　with　3d-4f　vertices　synthesized　by　hierarchical　subcomponent　self-assembly　of　tris(2-aminoethyl)amine,　2,6-diformyl-p-cresol,　and　lanthanide　ions　(Ln)　with　different　amines　and　transition　metal　ions.　The　programmable　self-assembly　process　results　in　the　formation　of　triple-stranded　hetero-metallic　covalent　organic　discrete　complexes,　namely　3a-3c-(Ln,　Zn)　(Ln　=　SmIII,　EuIII,　DyIII,　YbIII　and　LuIII)　and　3a′-(Dy,　Co),　which　are　characterized　by　nuclear　magnetic　resonance　(NMR)　analysis,　electrospray　ionization　time-of-flight　mass　spectrometry　(ESI-TOF-MS),　and　single-crystal　X-ray　analysis.　Photophysical　investigations　disclose　that　the　organic　skeleton　of　3a-(Ln,　Zn)　exhibits　an　excellent　sensitizing　ability　toward　SmIII,　EuIII,　and　YbIII　ions,　displaying　characteristic　luminescence　emission　in　both　the　visible　and　near-infrared　(NIR)　regions.　AC　susceptibility　measurements　of　3a′-(Dy,　Co)　reveal　the　frequency-independent　performance　under　zero　dc　field,　suggesting　the　absence　of　slow　relaxation　of　magnetization.　This　work　offers　a　new　approach　for　the　fabrication　of　discrete　metallic　covalent　architectures　with　3d-4f　vertices.　©　2023　The　Royal　Society　of　Chemistry.