Surface pressure (II) vs surface area (A) isotherms of dihexadecyl phosphate (DHP) monolayers floating on aqueous tris(2,2'-bipyridyl)ruthenium(II) chloride ([Ru(bpy)(3)][Cl-2]) solutions have established the formation of liquid expanded (LE), liquid condensed (LC), and solid condensed (SC) phases. Repeated compression and expansion cycles lead to the irreversible formation of a SC phase. Horizontal lifting of a hydrophilic substrate through the monolayer resulted in the transfer of a layer of DHP-coated [Ru(bpy)(3)](2+) microcrystallites. Additional layers of DHP/[Ru(bpy)(3)](2+) micocrystallites have been transferred by Schaefer's method. The presence of [Ru(bpy)(3)](2+) microcrystallites in the transferred multilayers has been established by absorption and fluorescence spectroscopies. The absorption and emission spectra of [Ru(bpy)(3)](2+) microcrystallites, grown under the DHP monolayers, had their maxims red-shifted and blue-shifted with respect to those observed for [Ru(bpy)(3)][Cl-2] in aqueous solution. Near-field scanning optical microscopy (NSOM) has been employed to spatially and spectrally resolve, at a submicron resolution, the presence of isolated seed crystals and their growth into differently shaped [Ru(bpy)(3)](2+) microcrystallites. NSOM also provided information on domain boundaries and on the partitioning of the fluorescent species into the various phases in the monolayer. Site-resolved near-field fluorescence spectroscopy provided evidence for the presence of [Ru(bpy)(3)](2+) microcrystallites in the circular domains formed under a DHP monolayer.