The first example of a lanthanide tetrakis(dithiolene) complex, [Na-5(THF)(10)Ce(mnt)(4)] (1) (mnt = 1,2-maleonitrile-1,2-dithiolate), has been synthesized and characterized by X-ray crystallography and spectroscopic methods. In the solid state, 1 exists as a 2-D corrugated honeycomb network polymer in which the monomeric units comprising the trigonal nodes are knitted together by interlocking dative Na-N bonds extended from nitrile groups of bifunctional mnt ligands coordinated through the sulfur atoms to adjacent cerium centers. Individual honeycomb sheets are separated by 14.8 angstrom. Compound 1 dissolves in donor solvents such as THF and acetonitrile to give soluble [Ce(mnt)(4)](5)-units that exhibit spectroscopic features (i.e., NMR, luminescence, UV-vis) that are consistent with the 4f(1) Ce(III) ion. In the first examination of the redox chemistry of a lanthanide dithiolene complex, cyclic voltammetry measurements conducted on 1 reveal a single irreversible oxidation wave that is likely attributable to ligand-centered oxidation.