Self-assembled multilayer films of polyethyleneimine/mixed (Ca, Mg, and Eu) hydroxides were fabricated on a quartz glass substrate by an alternating layer-by-layer (LBL) deposition method. X-ray diffraction and scanning electron microscopy analyses revealed that calcination of the multilayer films at 1100 degrees C in a reducing atmosphere resulted in the formation of dense CaMgSi2O6 films due to extensive reaction between the deposited hydroxide particles and the substrate. The films thus obtained showed intense blue emission peaking at 450 nm, ascribable to the 4f(7)-4f(6)5d transition of Eu2+ ions, when excited at 359 nm, suggesting the formation of Eu2+-doped CaMgSi2O6 phosphor films on the quartz glass substrate. Furthermore, they showed higher emission intensities than the commercial BaMgAl10O17:Eu2+ phosphor powder used as a reference. This study thus showed that the developed LBL method is a promising route for preparing efficient alkaline earth silicate-based phosphor films.