Understanding the luminescence mechanisms and regulating the emission centers of carbon dots (CDs) are important for advancing their related applications. In this work, we systematically investigate the formation processes of multi-emission centers in CDs synthesized through a bottom-up approach by controlling the solvothermal reaction temperature. CDs synthesized at a lower temperature (140 °C, 140-CDs) exhibit smaller particle sizes (3–4 nm) with dominant green–yellow emission, while CDs synthesized at a higher temperature (180 °C, 180-CDs) exhibit larger particle sizes (8–9 nm) with enhanced red emission and emerging near-infrared (NIR) emission. The green–yellow emission and red emission originate from the core state and the surface-related state, respectively, and the emissions could be regulated by temperature-controlled dehydration and carbonization processes. The clear NIR emission center in 180-CDs is attributable to the increased content of radical defects in the cores during the increased dehydration and carbonization processes during higher-temperature solvothermal treatment.