Tessellation of self-assembling molecular building blocks is a promising strategy to design metal-organic materials exhibiting geometrical frustration and ensuing frustrated physical properties. Appearing in two-dimensional quasiperiodic phases, tilings consisting of five-vertex nodes are regarded as approximants for quasicrystals. Unfortunately, these structural motifs are exceedingly rare due to the complications of acquiring five-fold coordination confined to the plane. Lanthanide ions display the sufficient coordinative plasticity, and large ionic radii, to allow their incorporation into irregular molecule-based arrays. We herein present the use of ytterbium(II) as a five-vertex node in a two-dimensional coordination solid, YbI2(4,4'-bipyridine)2.5. The semi-regular Archimedean tessellation structure verges on quasicrystallinity and paves the way for lanthanide-based metal-organic materials with interesting photonic and magnetic properties.