Luminescent carbon nanostructures (CNSs) have been intensively researched, but there is still no consensus on a fundamental understanding of their structure and properties that limits their potential applications. In this study, we developed a facile approach to the synthesis of luminescent composite SiO2 nanoparticles/CNSs by the targeted formation of a molecular fluorophore, as the significant luminescent component of CNSs, on the surface of a silica matrix during a one-stage hydrothermal synthesis. Silica nanoparticles were synthesized by reverse microemulsion and used as a matrix for luminescent composites. The as-prepared silica nanoparticles had a functional surface, a spherical shape, and a narrow size distribution of about 29 nm. One-stage hydrothermal treatment of citric acid and modified silica nanoparticles made it possible to directly form the luminescent composite. The optical properties of composites could be easily controlled by changing the hydrothermal reaction time and temperature. Thus, we successfully synthesized luminescent composites with an emission maximum of 450 nm, a quantum yield (QY) of 65 ± 4%, and an average size of ~26 nm. The synthesis of fluorophore doped composite, in contrast to CNSs, makes it possible to control the shape, size, and surface functionality of particles and allows for avoiding difficult and time-consuming fractionation steps.