The synthetic origin of nanocarbon and its role on the luminescence properties of carbon nanodots, in particular, citric acid derived ones, remain an enigma to date. We report here, for the very first time, that citrazinic acid alone builds a nanocarbon structure upon incubation in dimethylformamide at room temperature. The emission properties of incubated fluorophore resemble that of a nanodot. The dispersion of the H-bonded cluster’s size originated from citrazinic acid only is the cause of excitation-dependent emission. We have shown that the steric hindrance caused by the presence of alkyl chain of butyl amine restricts such dispersions, resulting in excitation-independent emission, a molecular behavior. On the other hand, for achieving white-light emission through a one-step method, the solvothermal reaction of citric acid with ammonium thiocyanate has been performed. The ground-state heterogeneity and luminescence properties are strongly influenced by the solvent polarity. We identify the existence of blue-, green-, and red-emissive fluorophores in a product obtained from solvothermal reaction. The computed vertical excitations of the molecular fluorophore predicted by the reaction mechanism are in good agreement with the experimental observations. Unprecedently, a product-embedded PVA/PVP film exhibits white light emission under irradiation of UV light, 365 nm. The mechanism of white light emission is attributed to effective energy transfer among fluorophores.