The self-assembly of the lanthanide metal−organic frameworks presents a formidable challenge but profound significance. Compared with the metal−organic frameworks based on 4f−3d ions, the chemistry of 4f−3p metal−organic frameworks has not been fully explored so far. In this study, two lanthanide− aluminum-based clusters [Ln 6 Al(IN) Ln = Gd, abbreviated as Gd 6 Al; x = 2.5, Ln = Eu, abbreviated as Eu 6 Al; HIN = isonicotinic acid) have been meticulously designed and obtained by hydrothermal reaction at low pH. The crystallographic study revealed that both Gd 6 Al and Eu 6 Al clusters exhibit an unprecedented sandwiched metal−organic framework holding a highly ordered honeycomb network. To our knowledge, it is the first case of Ln−Al-based cluster-organic frameworks. Furthermore, magnetic investigation of Gd 6 Al manifests a decent magnetic entropy change of −ΔS m max = 28.8 J kg −1 K −1 at 2 K for ΔH = 7.0 T. Significantly, the introduction of Al III ions into the lanthanide metal−organic frameworks displays excellent solid-state luminescent capability with a lifetime of 371.6 μs and quantum yield of 6.64%. The construction and investigation of these two Ln−Al clusters represent great progress in the 4f−3p metal−organic framework.