Controlling mechanisms involved in the aggregation of carbon quantum dots (CQDs) can lead to new application developments for these quantum dot materials. In this study, an unusual aggregation-induced white emission of CQDs with strong intrinsic green emission is reported. Due to the deprotonation/protonation of the surface functional groups during the aggregation of CQDs induced by pH variations of the solution through the addition of sodium hydroxide, and hydrophobic interactions between CQDs, it results in the formation of aggregated CQDs through an avalanche-like process. Our results suggest that sodium hydroxide not only plays a critical role in the formation of strong cation–π interactions, but also polishes the surface of CQDs, leading to the formation of the aggregated CQDs. The aggregated CQDs present excellent dispersibility characteristics in water. Moreover, optical studies suggest a combined aggregation mechanism in the presence of both J-type and H-type aggregation monoliths involved in forming the aggregated CQDs. The findings obtained from the deconvolution of the as-synthesized CQDs can perceptively elucidate the cation–π aggregation process.