Although mechanically interlocked molecules (MIMs) display unique properties and functions associated with their intricate connectivity, limited assembly strategies are available for their synthesis. Herein, we presented a synergistic assembly strategy based on coordination and noncovalent interactions (π–π stacking and CH⋯π interactions) to selectively synthesize molecular closed three-link chains ( 613 links), highly entangled figure-eight knots ( 41 knots), trefoil knot ( 31 knot), and Borromean ring ( 623 link). 613 links can be created by the strategic assembly of nonlinear multicurved ligands incorporating a furan or phenyl group with the long binuclear half-sandwich organometallic Cp*Rh III (Cp* = η 5 -pentamethylcyclopentadienyl) clip. However, utilizing much shorter binuclear Cp*Rh III units for union with the 2,6-naphthyl-containing ligand led to a 41 knot because of the increased π–π stacking interactions between four consecutive stacked layers and CH⋯π interactions. Weakening such π–π stacking interactions resulted in a 31 knot. The universality of this synergistic assembly strategy for building 41 knots was verified by utilizing a 1,5-naphthyl-containing ligand. Quantitative conversion between the 41 knot and the simple macrocycle species was accomplished by adjusting the concentrations monitored by NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS). Furthermore, increasing the stiff π-conjugated area of the binuclear unit afforded molecular Borromean ring, and this topology is a topological isomer of the 613 link. These artificial metalla-links and metalla-knots were confirmed by single-crystal X-ray diffraction, NMR and ESI-MS. The results offer a potent strategy for building higher-order MIMs and emphasize the critical role that noncovalent interactions play in creating sophisticated topologies.