A photoluminescent‐based “Turn On → Off → On” technique was adopted for a toxic, heavy metal ion detection, that is, specifically chromium (VI) and a pharmaceutically relevant ascorbic acid molecule. Metal‐free, environmentally benign, and fluorescent carbon dots, a potential vehicle for spectrofluorometric detection, were successfully deployed as sensors. Carbon dots synthesized from citric acid and sulfanilamide conserve the fragments of the precursor molecule on the surface. Zeta potential measurement evidenced the positively charged carbon nanoparticles physically interact with the Cr(VI)/Cr2O72− in acidic pH, resulting in a remarkable quenching in net fluorescence. Thorough studies revealed that the static quenching and inner filter effect were responsible for the reduction in fluorescence intensity. We have demonstrated a new rapid (in seconds) detection platform for Cr(VI) and ascorbic acid.