This invited feature article focuses on the chemical reactions involving the surface ions of colloidal quantum dots (Qdots). Emphasis is placed on ion-exchange, redox, and complexation reactions. The pursuit of reactions involving primarily the cations on the surface results in changes in the optical properties of the Qdots and also may confer new properties owing to the newly formed surface species. For example, the cation-exchange reaction, leading to systematic removal of the cations present on the as-synthesized Qdots, enhances the photoluminescence quantum yield. On the other hand, redox reactions, involving the dopant cations in the Qdots, could not only modulate the photoluminescence quantum yield but also give rise to new emission not present in the as-synthesized Qdots. Importantly, the cations present on the surface could be made to react with external organic ligands to form inorganic complexes, thus providing a new species defined as the quantum dot complex (QDC). In the QDC, the properties of Qdots and the inorganic complex are not only present but also enhanced. Furthermore, by varying reaction conditions such as the concentrations of the species and using a mixture of ligands, the properties could be further tuned and multifunctionalization of the Qdot could be achieved. Thus, chemical, magnetic, and optical properties could be simultaneously conferred on the same Qdot. This has helped in externally controlled bioimaging, white light generation involving individual quantum dots, and highly sensitive molecular sensing. Understanding the species (i.e., the newly formed inorganic complex) on the surface of the Qdot and its chemical reactivity provide unique options for futuristic technological applications involving a combination of an inorganic complex and a Qdot.