range (NIR-I region: 700-900 nm; NIR-II region: 1000-1700 nm). [15][16][17][18][19][20] Deep tissue penetration can be realized in this spectral range owing to the low degree level of photon absorption, scattering, and autofluorescence from tissues. [21,22] Therefore, imaging and therapeutic agents which operate in the DR to NIR region are highly desired. For CDs, strong PL in the blue and green region has been reported on numerous occasions, with PL quantum yields (QY) up to 90%, [23,24] while CDs with efficient longer wavelength emission have experienced extensive development only recently. Starting from the first report on the orange emissive CDs (PL peak at 580 nm) with a PL QY of 46%, [25] red emissive CDs with PL peak at 628 nm and PL QY of 53%, [26] and NIR emissive CDs with PL peak at 715 nm and PL QY of 43% [27] were introduced. A number of strategies, such as enlarging the π-conjugated structure, enhancing the surface oxidation, and employing proper precursors such as phenylenediamines were proved as effective for realization of such CDs. This review starts from summary of synthetic strategies toward CDs with absorption/PL at the wavelength from 650 nm and into the NIR-I and NIR-II spectral region. We then consider in detail the Stokes and anti-Stokes PL (ASPL), chemiluminescence (CL) and formation of reactive oxygen species (ROS) for the DR/NIR CDs. At the end, we provide a concise summary of already reported biomedical applications of CDs, such as in the photoacoustic (PA) imaging and photothermal therapy (PTT), photodynamic therapy (PDT), and their use as bioimaging agents and drug carriers.Carbon dots (CDs) represent a recently emerged class of luminescent materials with a great potential for biomedical theranostics, and there are a lot of efforts to shift their absorption and emission toward deep-red (DR) to near-infrared (NIR) region falling in the biological transparency window. This review offers comprehensive insights into the synthesis strategies aimed to achieve this goal, and the current approaches of modulating the optical properties of CDs over the DR to NIR region. The underlying mechanisms of their absorption, photoluminescence, and chemiluminescence, as well as the related photophysical processes of photothermal conversion and formation of reactive oxygen species are considered. The already available biomedical applications of CDs, such as in the photoacoustic imaging and photothermal therapy, photodynamic therapy, and their use as bioimaging agents and drug carriers are then shortly summarized.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/smll.202102325. Figure 12. a) In vivo NIR fluorescence images of a mouse stomach before (left) and after (right) gavage injection of CDs in PVP aqueous solution.Reproduced with permission. [46] Copyright 2018, Wiley-VCH. b) NIR fluorescence images of mouse tumor after intravenous injection of CDs at various time points. c) NIR fluorescence of H22 tumors that were dissected from mice at ...