An unusual aggregation phenomenon that involves positively charged poly(L-lysine) (PLL) and negatively charged gold nanoparticles (Au NPs) is reported. Discrete, submicrometer-sized spherical aggregates are found to form immediately upon combining a PILL solution with gold Sol (diameter; approximate to 14 nm). These PLL-Au NP assemblies grow in size with time, according to light scattering experiments, which indicates a dynamic flocculation process. Water-filled, silica hollow microspheres (outer diameter approximate to microns) are obtained upon the addition of negatively charged SiO2 NPs (diameter approximate to 13 nm) to a suspension of the PLL-Au NP assemblies, around which the SiO2 NPS form a shell. Structural analysis through confocal microscopy indicates the PLL (tagged with a fluorescent dye) is located in the interior of the hollow sphere, and mostly within the silica shell wall. The hollow spheres are theorized to form through flocculation, in which the charge-driven aggregation of Au NPs by PLL provides the critical first step in the two-step synthesis process ("flocculation assembly"). The SiO2 shell can be removed and re-formed by decreasing and increasing the suspension pH about the point-of-zero charge of SiO2, respectively.