A bottom-up method, using monoethanolamine (MEA) as both a passivation agent and a solvent, has been developed for rapid and massive synthesis of nitrogen-doped carbon dots (N-C-dots) from citric acid under heating conditions. This method requires relative mild temperature (170 °C) without special equipment, and affords one-pot large-scale production (39.96 g) of high-quality N-C-dots (quantum yield 10 of 40.3%) in a few minutes (10 minutes). Significantly, an interesting formation process of N-C-dots, for the first time, has been monitored by transmission electron microscopy, ultraviolet-visible absorbance spectroscopy, photoluminescence spectroscopy, Fourier transformed infrared spectroscopy, and thermogravimetric analysis, and a corresponding formation mechanism including polymerization, aromatization, nucleation, and growth, is proposed. It is important that the MEA-based synthesis of N-C-15 dots can be extended to various precursors, such as glucose, ascorbic acid, cysteine, and glutathione, which show general university. Furthermore, the N-C-dots with strong fluorescence, excellent optical stability, and low cytotoxicity, are successfully applied as fluorescent probes for bioimaging.