Development of the methods to organize zeolite microcrystals into closely packed and uniformly aligned monolayers on various substrates have been pursued viewing microparticles as a novel class of building blocks. We now report that the vertically aligned zeolite monolayer can be applied as novel supramolecularly organized systems for anisotropic photoluminescence in high dichroic ratio, to study energy transfer dynamics between the internal and external fluorophores, and to develop zeolite-based advanced materials. Study of polarized fluorescence spectroscopy and angle-dependent intensity change with dye molecules in different surroundings further provides insight into molecular interactions that can be used for the future design of optoelectronic device in nanometer size. In addition, this report shows that isolating of organic dye through surface treatment is crucial for preventing the egress of the incorporated dye molecules from the channels of zeolite to the solution and to enhance the anisotropic luminescence.