Heterovalent doping in colloidal semiconductor nanocrystals (CSNCs), with provisions of extra electrons (n-type doping) or extra holes (p-type doping), could enhance their performance of optical and electronical properties. In view of the challenges imposed by the intrinsic self-purification, self-quenching, and self-compensation effects of CSNCs, we outline the progress on heterovalent doping in CSNCs, with particular focus on the cation-exchange-enabled tuning of dopant luminescence and electronic impurities. Thus, the well-defined substitutional or interstitial heterovalent doping in a deep position of an isolated nanocrystal has been fulfilled. We also envision that new coordination ligand-initiated cation exchange would bring about more choices of heterovalent dopants. With the aid of high-resolution characterization methods, the accurate atom-specific dopant location and distribution could be confirmed clearly. Finally, new applications, some of the remaining unanswered questions, and future directions of this field are presented.