The adduct Eu(NTA)3 · bipy was prepared by the reaction of Eu(NTA)3 · 2H2O with 2,2′-bipyridine in a 1:1 ratio in chloroform [NTA = 1-(2-naphthoyl)-3,3,3-trifluoroacetonate]. Recrystallization of the complex from a chloroform/diethyl ether solvent mixture gave crystals suitable for X-ray diffraction. The structure contained chloroform molecules in partially occupied sites and was found to be different from the two forms previously reported for the same adduct (one unsolvated and the other containing isopropanol molecules). A single eight-coordinate geometry was found for Eu(NTA)3 · bipy · 0.44CHCl3, corresponding to a distorted square antiprism, with the bidentate ligands spanning opposite sides of the ‘square’ faces. A 2:1 (host-to-guest) inclusion compound comprising β-cyclodextrin (CD) and Eu(NTA)3 · bipy was obtained by co-precipitation from a mixed water/ethyl acetate solvent mixture. The formation of a true inclusion complex was supported by powder XRD, thermogravimetric analysis and 13C CP MAS NMR spectroscopy. Photoluminescence spectroscopy indicated the presence of only one low-symmetry environment for the Eu3+ cations in non-included Eu(NTA)3 · bipy and the inclusion compound. However, upon encapsulation of the complex in β-CD, some of the Eu3+ intra-4f6 5D0 → 7F0–4 lines shifted in energy, and the number of Stark components for the 5D0 → 7F1–2 transitions increased, indicating a lowering of the symmetry of the Eu3+ local coordination environment. The room temperature excitation spectrum of the inclusion compound revealed an enhancement of the Eu3+ sensitized process as a result of encapsulation of the Eu(NTA)3 · bipy molecules.