The mechanism of intrinsic fluorescence of carbon dots (CDs), the latest nanomaterial from the carbon family, was supposedly deciphered through multiple theories. However, the much sought-after persistent red emission of CDs as a foreseeable consequence of experiments remains elusive prompting the question of whether tuning of the red emission of CDs is a predictable outcome or a serendipitous coincidence. Herein, we tried to decode the same by exploring Alizarin Red S (ARS)-based red emitting CDs in different solvents with wisely chosen analytical tools. The findings are aptly supported by molecular dynamics studies through an experimental intuition-driven model-building approach. Parallel interception of the CDs with powder X-ray diffraction (pXRD) and photophysical spectroscopic studies revealed an important relationship between the solvent and CDs. Tautomerism, a well-known phenomenon with chemical entities, was found to be operative for CDs that greatly influence the Stokes shift and ultimately the fluorescence outcome. Most importantly, pXRD studies established the turbostratism of the CDs where the well-ordered graphitic structure of CDs gets disrupted with solvent molecules. The extent of such disruption is a function of solvent and CD composition that plays a formidable role in obtaining red fluorescence. Thus, for the first time, we demonstrate that the red emission of CDs is related to its structural integrity and if taken care of could be sustained, a tremendously desirable outcome for relevant applications.