Epitaxial multilayers of 2,9-di(2-hydroxyethyl)-anthra[2,1,9-def:6,5,10-d 'e 'f]diisoquinoline-1,3,8,10-tetrone (DMe-PTCDI) were prepared on epitaxially grown phthalocyanine copper(ll) complex (CuPc) multilayers on Ag(110) by molecular beam epitaxy. This work presents LEED and photoluminescence investigations of a highly ordered organic heterosystem. Four different mono- and multilayer structures are presented. LEED images taken during preparation of the monolayer structures show a dose-dependent structural phase transition. Photoluminescence measurements on the heterosystem show a temperature-dependent transition in the fluorescence spectrum, resulting in a significant intensity increase. The results are compared to a previous study of DMe-PTCDI on Ag(110).