1-Trifluoromethyl-3-[2.2]metacyclophanyl-1,3-propanedione (HtfacacMCP) which has a non-planar conjugated π system and 1-trifluoromethyl-3-(p-tolyl)-1,3-propanedione (p-tolutfacacH) as the referential ligand were prepared. Complexation of these ligands with europium(III) chloride in the presence of bipyridine (bpy) gave (tfacacMCP) 3 (bpy)Eu(III) and piperidinium[(p-tolutfacac) 4 Eu(III)] complexes respectively. The X-ray crystal structure of (tfacacMCP) 3 (bpy)Eu(III) revealed an eight-coordinate configuration with two N atoms of bpy and six O atoms of HtfacacMCP. On the other hand, piperidinium[(p-tolutfacac) 4 Eu(III)] was found to be an eight-coordinate complex surrounded by eight O atoms of p-tolutfacacH. The former contains bpy, but the latter contains no bpy.