Recently, the chemiluminescence (CL) induced by carbon nanodots (CDs) has intrigued researchers’ extensive interests in various applications due to its special light emission principle. However, the difficulty of synthesizing chemiluminescent CDs with full-spectrum emission severely hinders the further regulation of the CL emission mechanism. Herein, the multi-color-emissive chemiluminescent CDs are rational designed and further synthesized by regulating the sp²-hybrid core and sp³-hybrid surface from the citrate-ammonia molecular in a single solvothermal reaction. More experimental characterizations and density functional theory calculations reveal that the higher temperature can promote the crosslinking polymerization/carbonization of carbon core and the higher protonation of solvent can determine the core size of final CDs, resulting in the variant CL emission from molecular-, crosslinking- and core-states. Thus, the CL emission of the CDs can be further synthesized by tuning the luminescence chromophores in the formation process via regulating the temperature and solvent, enabling the applications of the CL CDs in illumination and information encryption. This study paves a new technology to understand the luminescence of CDs and affords an industry translational potential over traditional chemiluminescent molecular.