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Through an “isoreticular expansion” strategy, a large number of highly porous zirconium-based metal–organic frameworks (Zr-MOFs) have been achieved using extended organic linkers in the past few years. However, interpenetrated Zr-MOFs with ftwtopology have scarcely been reported, mainly owing to the used bulky tetratopic linkers that effectively prevent the network interpenetration. Here, we report a new family of zirconium and lanthanide (Ln) MOFs with ftwtopology, constructed by hexanuclear Zr or Ln (Ln = Eu, Tb, Gd, Dy, Tm, Yb, Nd, and Er) clusters and a spirobifluorene-center tetracarboxylate linker. Our studies reveal that the isostructural Zr and Ln MOFs are all doubly interpenetrated with ultrahigh thermal and chemical stability. The observed unusual interpenetration can be attributed to the specific geometry of the spirobifluorene-center tetratopic linker. Gas adsorption studies show that the interpenetrated Zr-MOF is still highly porous and exhibits high performance for CO2storage, which can be attributed to the strong CO2binding environment contributed by the reduced pore size. In addition, the presented MOFs display strong characteristic luminescence in the UV–vis–NIR region. Moreover, the incorporation of the spiro-center linker into the framework can efficiently produce two-photon-excited photoluminescence with a large action cross-section value, which also benefited from the high packing density of the nonlinear optical chromophore linker in the interpenetrated structure.