The endohedral fullerene Er3N@C-80 shows characteristic 1.5 mu m photoluminescence at cryogenic temperatures associated with radiative relaxation from the crystal-field split Er3+ I-4(13/2) manifold to the I-4(15/2) manifold. Previous observations of this luminescence were carried out by photoexcitation of the fullerene cage states leading to relaxation via the ionic states. We present direct non-cage-mediated optical interaction with the erbium ion. We have used this interaction to complete a photoluminescence-excitation map of the Er3+4I13/2 manifold. This ability to interact directly with the states of an incarcerated ion suggests the possibility of colierently manipulating fullerene qubit states with light. (c) 2006 Elsevier B.V. All rights reserved.