In this study, we report that both CN⁻ and I⁻ can enhance the fluorescent intensity of Hg²⁺–graphene quantum dots (Hg²⁺–GQDs). However, the selectivity of the sensor was poor. Accordingly, simple specific masking agents can be directly used to solve this problem. Here, for the first time, we report the use of persulfate ion (S₂O₈²⁻) as a turn-on fluorescent probe of Hg²⁺–GQDs for selective CN⁻ detection, while hydrogen peroxide (H₂O₂) was selected for its sensing ability towards I⁻ ion detection. Interestingly, the signal was immediately measured after addition of the masking agent to Hg²⁺–GQDs and the sample because its interaction was very fast and efficient. The method had a linear response in the concentration ranges of 0.5–8 μM (R² = 0.9994) and 1–12 μM (R² = 0.9998) with detection limits of 0.17 and 0.20 μM for CN⁻ and I⁻, respectively. The sensor was successfully used for the dual detection of both CN⁻ and I⁻ in real water samples with satisfactory results. In conclusion, the specific masking agents in a Hg²⁺–GQDs system appeared to be good candidates for fluorometric “turn-on” sensors for CN⁻ and I⁻ with excellent selectivity over other ions.