In this paper, we report the discovery of superconductivity in Li 3 Ca 2 C 6 . Several graphite intercalation compounds (GICs) with electron donors, are well known as superconductors [T. Enoki, S. Masatsugu, E. Morinobu, Graphite Intercalation Compounds and Applications, Oxford University Press, Oxford, 2003]. It is probably not astonishing, since it is generally admitted that low dimensionality promotes high superconducting transition temperatures. Superconductivity is lacking in pristine graphite, but after charging the graphene planes by intercalation, its electronic properties change considerably and superconducting behaviour can appear. Li 3 Ca 2 C 6 is a ternary GIC [S. Pruvost, C. Hérold, A. Hérold, P. Lagrange, Eur. J. Inorg. Chem. 8 (2004) 1661–1667], for which the intercalated sheets are very thick and poly layered (five lithium layers and two calcium ones). It contains a great amount of metal (five metallic atoms for six carbon ones). Its critical temperature of 11.15K is very close to that of CaC 6 GIC [T.E. Weller, M. Ellerby, S.S. Saxena, R.P. Smith, N.T. Skipper, Nat. Phys. 1 (2005) 39–41; N. Emery, C. Hérold, M. d’Astuto, V. Garcia, Ch. Bellin, J.F. Marêché, P. Lagrange, G. Loupias, Phys. Rev. Lett. 95 (2005) 087003] (11.5K). Both CaC 6 and Li 3 Ca 2 C 6 GICs possess currently the highest transition temperatures among all the GICs.