Abstract Carbon nanomaterials have attracted the attention of the scientific community for more than 30 years now; first with fullerene, then with nanotubes and now with graphene and graphene related materials. Graphene quantum dots (GQDs) are nanoparticles of graphene that can be synthesized following two approaches, namely top‐down and bottom‐up methods. The top‐down synthesis used harsh chemical and/or physical treatments of macroscopic graphitic materials to obtain nanoparticles, while the second is based on organic chemistry through the synthesis of polycyclic aromatic hydrocarbons exhibiting various sizes and shapes that are perfectly controlled. The main drawback of this approach is related to the low solubility of carbon materials that prevents the synthesis of nanoparticles containing more than few hundreds of sp 2 carbon atoms. Here we report on the synthesis of a family of rectangular‐shaped graphene quantum dots containing up to 162 sp 2 carbon atoms. These graphene quantum dots are not functionalized on their periphery in order to keep the maximum similarity with nanoparticles of pure graphene. We chose water with sodium deoxycholate surfactant to study their dispersion and their optical properties (absorption, photoluminescence and photoluminescence excitation). The electronic structure of the particles and of their aggregates are studied using Tight‐Binding (TB). We observe that the larger particles ( GQD 3 and GQD 4 ) present a slightly better dispensability than the smaller ones, probably because the larger GQDs can accommodate more surfactant molecules on each side, which helps to stabilize their dispersion in water.