Precise　topological-structural　control　over　bismuth-based　metal-organic　frameworks　(Bi-MOFs)　is　hampered　by　the　challenge　of　balancing　thermodynamics　and　kinetics.　Such　balance　is　achieved　in　three　well-defined　Bi-MOFs　with　crystalline,　semi-crystalline,　and　amorphous　topologies　via　a　straightforward　secondary　building　unit　approach　in　bismuth-2-aminoterephthalic　acid　(Bi-BDC-NH2).　The　structure　of　Bi-BDC-NH2　is　confirmed　by　single-crystal　X-ray　diffraction　(XRD)　to　consist　of　BiO9　nodes.　The　amount　of　2-aminoterephthalic　acid　is　varied　to　modulate　the　topology　via　competitive　complexation　and　thus　control　the　thermodynamic　and　kinetic　nucleation　products.　Through　regulating　the　ligand-to-metal　ratio　of　H2BDC-NH2　to　Bi,　an　appropriate　balance　of　the　thermodynamic-versus-kinetic　structural　＂trade-off＂　is　achieved.　The　fine　topologies　of　Bi-MOFs　are　determined　by　single-crystal　XRD,　high-resolution　transmission　electron　microscopy,　X-ray　photoelectron　spectroscopy,　and　X-ray　absorption　fine　structure.　For　the　first　time,　it　is　reported　that　applying　Bi-MOFs　with　varying　topological　structures　as　photocatalysts　for　removing　nitric　oxide　(NO)　demonstrates　that　the　amorphisation　improves　the　photogenerated　charge　separation　efficiency　and　adsorption　and　activation　of　O2.　This　work　offers　a　guide　in　complex　topological-structural　control,　which　is　conducive　for　those　to　develop　highly　efficient　MOFs-based　photocatalysts.