The new ternary gallide Eu3Li5+xGa5–x was synthesized from its constituent elements that were heated at 900 °C and then subsequently annealed at 300 °C for 10 months. The crystal structure was established from single-crystal diffraction data. A new type of discrete gallium cluster was found inEu3Li5+xGa5–x, namely a bell-like [Ga5] unit with one single-,one four- and three three-bonded atoms. On the basis of its structural features, magnetic properties and calculated electronic density of states (DOS), the title compound is represented as [Eu2+]3[Li+]5[(1b)Ga4–]1[(3b)Ga2–]3[(4b)Ga1–]1 (xb = number of bonds, where x = 1–4). The new structural unit observed in this compound is compared with other [Gan] (n = 2–6) clusters found in binary gallium compounds.