Si quantum dots (SiQDs) based nanospheres (SiNSs) were prepared via a novel synthetic strategy. These SiNSs were demonstrated to possess unique dot spacing dependent photoluminescence (PL) up-conversion and surface dependent (N modified surface) down-converted PL. It was demonstrated that a small distance between SiQDs (<5 nm) is the necessary condition for the PL up-conversion of SiNSs, while the surface state of SiQDs will affect the maximum emission wavelength and the PL intensity. The as-prepared SiNSs feature excellent aqueous dispersibility, and their optical properties were found to be stable enough in a specified temperature and pH range.