A novel N-substituted 4-methoxy-1,8-naphthalimide (NAFTA 8) especially designed for fluorescent labeling of gold nanoparticles has been synthesized. NAFTA 8 bears a long methylene chain at the imide N atom and has a terminal SH group, which enables its chemical binding to gold nanostructures. The longest wavelength absorption maximum of NAFTA 8 in chloroform is at 370 nm, the fluorescent maximum is at 430 nm and the fluorescent quantum yield is 0.95. The newly synthesized fluorophore is applied for functionalization of gold nanoparticles with diameter 1.5 ± 0.5 nm prepared through chemical reduction. The obtained Monolayer Protected Clusters are characterized by elemental analysis, TEM, XPS, FT-IR, absorption and fluorescence spectroscopy. The performed investigations provide evidence for the formation of chemical bond between the thiol ligand and the gold surface. They also show that the obtained metal/dielectric 3D structures are highly fluorescent.