As a new kind of carbon based functional material, carbon dots (CDs) have sparked much interest in recent years. The tunable structure, composition, and morphology of CDs unlocks opportunities to enable diversity in their photoelectrochemical properties, and thus they show great potential in various applications such as biology, catalysis, sensors, and energy storage. Nevertheless, the related understanding of CDs is insufficient at present due to their inherent complexity of microstructure, which involves the intersection of high polymer, bulk carbon, and quantum dot (QD). A good understanding of the underlying mechanism behind the properties of CDs is still a formidable challenge, requiring the integration of robust knowledge from organic chemistry, materials science, and solid state physics. Within this context, discovering more appealing properties, elucidating fundamental factors that affect the properties and proposing effective engineering strategies that can realize specific functions for CDs are now highly pursued by researchers.At the beginning of this Account, the main features of CDs are introduced, where not only the basic structural, compositional and morphological characteristics but also the rich photoelectrochemical properties are elucidated, among which the band gap, chirality, photoinduced potential, and electron sink effect are particularly emphasized. Furthermore, new analysis techniques including transient photoinduced current (TPC), transient photoinduced voltage (TPV), and machine learning (ML) to reveal the unique properties of CDs are described. Then, several appealing strategies that aim to rationally tailor CDs for oriented applications are highlighted. These regulation strategies are morphology modulation (e.g., developing CDs with new geometrical configuration, controlling the particle size), phase engineering (e.g., altering the phase crystallinity, introducing the foreign atoms), surface functionalization (e.g., grafting various types of functional groups), and interfacial tuning (e.g., building CD-based nanohybrids with well-defined interfaces). Although the fundamental investigation of CDs is relatively undeveloped because of their complexity, this does not hinder their wide application. At the same time, exploring the extensive applications of CDs will promote their in-depth understanding. Finally, the chances for building a CD-centered blueprint for sustainable society are explored and challenges for future research in the field of CDs are proposed as follows: (i) the controllable synthesis of CDs with uniform size; (ii) search for novel CDs with unique structure, morphology, or composition; (iii) quantitative understanding of the property of CDs; (iv) performance enhancement by external forces such as magnetism or heat injection; (v) construction of the dual carbon concept; (vi) further research on different photocatalytic applications. On the whole, this Account may provide meaningful references for the understanding of the microstructure-property correlation as well as the regulation of CDs, thereby promoting their transition from fundamental research to practical application.