Nitrogen-doped carbon nanodots (CNDs) were synthesized and utilized as sensing probes to detect different anions and metallic ions within aqueous solutions. The pristine CNDs were developed through a one-pot hydrothermal synthesis.o-Phenylenediamine was used as the precursor. A similar hydrothermal synthesis technique in the presence of polyethylene glycol (PEG) was adopted to form the PEG-coated CND clusters (CND-100k). Through photoluminescence (PL) quenching, both CND and PEG-coated CND suspensions display ultra-high sensitivity and selectivity towards HSO4−anions (Stern–Volmer quenching constant (KSV) value: 0.021 ppm−1for CND and 0.062 ppm−1for CND-100k) with an ultra-low detection limit (LOD value: 0.57 ppm for the CND and 0.19 ppm for CND-100k) in the liquid phase. The quenching mechanism of N-doped CNDs towards HSO4−ions involves forming the bidentate as well as the monodentate hydrogen bonding with the sulfate anionic moieties. The detection mechanism of metallic ions analyzed through the Stern–Volmer formulation reveals that the CND suspension is well suited for the detection of Fe3+(KSVvalue: 0.043 ppm−1) and Fe2+(KSVvalue: 0.0191 ppm−1) ions, whereas Hg2+(KSVvalue: 0.078 ppm−1) sensing can be precisely performed by the PEG-coated CND clusters. Accordingly, the CND suspensions developed in this work can be employed as high-performance PL probes for detecting various anions and metallic ions in the liquid phase.