Our objectives are to provide a comprehensive review solely concerning the synthesis and chemistries of polyhedral phenylsilsesquioxanes. The review covers the basic efforts to synthesize and characterize the compounds [PhSiO1.5](8), [PhSiO1.5](10), and [PhSiO1.5](12). Thereafter, we discuss general methods of functionalizing these compounds with emphasis on electrophilic substitution to produce, for example, [NO2PhSiO1.5](8), [NO2PhSiO1.5](12), [p-iphsioO(1.5)](8), [p-IPhSiO1.5](10), [o-BrPhSiO1.5](8), [2,5Br(2)PhSiO(1.5)](8), and [Br3PhSiO1.5](8) as well as Friedel-Crafts alkylation products. Second-generation compounds and nanocomposite materials derived from these intermediates are also discussed in detail. The review ends with a discussion of the apparent. 3-D photophysical properties of third-generation functionalized phenylsilsesquioxanes.