Self-assembly of trans-{EuI₂} nodes and ditopic ligands leads to isoreticular 2D frameworks featuring a rare, non-kagome Archimedean tessellation. The topology and intra-layer Eu(II)–Eu(II) antiferromagnetic interactions provide the prerequisites for geometrical spin frustration, which, due to the spin state degeneracy, is key for novel phenomena such as enhanced magnetic refrigeration.