AbstractTwo discrete lanthanide complexes with bulky aromatic mixed‐ligands, {[La2(na)6(phen)2]·[La2(na)6(phen)2]} (1) and [La2(na)6(2,2′‐bipy)2] (2) (Hna = 1‐naphthoic acid, phen = 1,10‐phenanthroline, and 2,2′‐bipy = 2,2′‐bipyridine), have been synthesized under hydrothermal conditions and fully characterized by single‐crystal X‐ray crystallography, IR, elemental analysis, TG‐DTA and fluorescence spectra. Structure determination reveals that 1 contains two separate binuclear [La2(na)6(phen)2] units, in which both crystallographically LaIII ions are nine‐coordinated with tricapped trigonal prism polyhedron for La1 and a distorted monocapped square antiprism arrangement for La2; whereas 2 has a binuclear structure bridged by carboxylate groups of four na anions. Due to the introduction of bulky aromatic ligands, non‐classical C–H···O H–bonds and π – involved stacking interactions become the dominantly driving forces for the supramolecular structure. The two solid complexes exhibit intense fluorescent emissions at room temperature resulted from the ligand‐to‐metal charge transfer.