Using air as an insulator due to its low heat transfer coefficient has been studied and has been widely commercialized to save energy in the field of thermal insulation technology. In this study, we analyzed the heat insulating effect of hollow silica nanoparticles mixed in non-uniform size, and the maximum heat insulating efficiency of these particles given the limited number of particles that can be mixed with a medium such as paint. The hollow silica nanoparticles were synthesized via a sol-gel process using a polystyrene template in order to produce an air layer inside of the particles. After synthesis, the particles were analyzed for their insulation effect according to the size of the air layer by adding 5 wt % of the particles to paint and investigating the thermal insulation performance by a heat transfer experiment. When mixing the particles with white paint, the insulation efficiency was 15% or higher. Furthermore, the large particles, which had a large internal air layer, showed a 5% higher insulation performance than the small particles. By observing the difference in the insulation effect according to the internal air layer size of hollow silica nanoparticles, this research suggests that when using hollow particles as a paint additive, the particle size needs to be considered in order to maximize the air layer in the paint.