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Luminescent carbon dots (CDs) have received increasing attention from many fields during the past decade. Unfortunately, the luminescent mechanisms of CDs remain unclear due to insufficient experimental and theoretical knowledge, which significantly hinders the development of CDs with desired optical properties. Currently, surface states of CDs, which are based on synergistic hybridization between the carbon backbones and the connected functional groups, have been considered as the dominant luminescence origins. This tutorial paper, thus, aims to offer an overview of the key features on the surface of CDs, such as particle size, surface functional groups, defects and heteroatom doping, and their influences on the photoluminescence of CDs. In addition, optical characteristics of surface state-derived luminescence emissions of CDs are also summarized. Finally, the potential approaches of characterizing surface states of CDs are introduced, followed by an outlook of synthesizing high-quality CDs through modulation of the surface states.