The development of photoluminescent (PL) systems, displaying multiple stimuli-responsive emission color tuning, has been the pressing priority in the recent times due to their huge role in contemporary lighting and anticounterfeiting technologies. Acknowledging this importance, we present a simple and eco-friendly PL system showing emission color tuning in response to different stimuli, that is, the composition of the system, pH, excitation wavelength, and the temperature with the plus point of getting significantly pure white light emission (WLE). The novel system is fabricated from the aqueous mixture of three organic fluorophores, umbelliferone (UMB), fluorescein (FLU), and Rhodamine-B (RB). By varying the fluorophore composition in the mixture at pH 12, nearly pure WLE with a Commission Internationale d'Eclairage (CIE) 1931 profile of (0.33, 0.33) was obtained at the excitation wavelength of 365 nm, the sustainability of which was ensured by employing the micellar self-assemblies of tetradecyltrimethylammonium bromide (TTAB) molecules. Similar WLE was obtained under mildly acidic conditions (pH 6) but at the excitation wavelength of 330 nm. By proper tuning of pH and the wavelengths of the system to use it as a fluorescent ink, we found a remarkable and highly applicable phenomenon observed for the first time, that is, triple-mode orthogonal emission color tuning with white light ON/OFF switching. We validate the vital applicability of this phenomenon in protecting the authenticity of the document with its hard-to-counterfeit property. The applicability of this phenomenon is also explored by synthesizing PVA-based fluorescent films from the tri-fluorophore mixture. Moreover, the emission color of the PL system was explored lucidly for its temperature dependence owing to the thermal responsiveness of RB emission, where the PL system proves to be a full-color RGB system.