Electronic absorption, luminescence and laser excitation spectra of the complex ion Eu(N₃)₈^5- in single crystals of Cs₅Eu(N₃)₈ have been measured at temperatures down to 4 K. Although the crystal structure shows the presence of only one type of Eu(H₃)₈^5- complex ion, in which nearest N atoms form an approximate D_4d (square anti-prismatic) coordination polyhedron about the Eu atom, the spectra clearly show the presence of two distinct, but closely similar, types of Eu atoms. For one of these sites, emission from the ⁵D₀ state to all the expected crystal field states of the ⁷F_J(J=0-6) manifold and from the ⁵D₁ state to all of the ⁷F_J(J=0, 1, 2, 3) states is observed and, together with the absorption and the excitation spectra, permit the location of 56 of the 57 crystal field states expected below 23000 cm^-1.