A polyhedral oligomeric silsesquioxane (POSS)-based electroluminescent nanoparticle, POSS-NPA, which contains anthracenenaphthyl chromophores on each of its eight arms, was easily prepared via the hydrosilylation reaction between octakis(dimethylsiloxy)silsesquioxane and allyl-functionalized 9-naphthalene-2-yl-10-phenyl anthracene chromophores. POSS-NPA was completely soluble in common organic solvents such as chloroform, THF, toluene, p-xylene, and chlorobenzene, and showed good film-forming properties on a quartz plate or an indium tin oxide (ITO) plate, i.e., it has good solution processing properties. The UV-visible absorption and the photoluminescence (PL) emission maxima of POSS-NPA in chlorobenzene solution were found to be 378 nm and 433 nm while those of POSS-NPA in the solid state were 379 and 464 nm, respectively. An electroluminescent (EL) device with the configuration of ITO/PEDOT:PSS/POSS-NPA (50 nm)/BAIq (40 nm)/LiF (1 nm)/Al (120 nm) was also fabricated and the blue light emission was successfully obtained.