Luminescence and Raman crystal field transitions of Eu3+ ions in Eu2BaZnO5 are investigated in off-resonance conditions for several excitation energies. Luminescence peaks are identified and classified into two groups (transitions from D-5(0) and those from D-5(1) or D-5(2)) as a function of their relative intensity versus temperature. Crystal field parameters are found to be very similar for both europium sites. Raman crystal field transitions are studied as a function of temperature. The increase of their intensity when temperature is lowered is explained by the change of the ground state population. The behaviour of the luminescence at several excitation energies has been explained by means of second-order processes. The lattice phonons and thermal population of the lowest excited multiplets have a determining role in the excitation processes of Eu luminescence. (C) 1998 Elsevier Science S.A.