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A novel effective chemosensor HPHN, (E)-6-hydroxy-N'-((2-hydroxynaphthalen-1-yl)methylene) picolinohydrazide, was synthesized. HPHN sensed Fe3+/2+ with the changes of color from yellow to orange without obvious inhibition from other cations. In addition, HPHN could detect ClO- by both the color change from yellow to colorless and the fluorescence quenching. The binding modes of HPHN with Fe3+/2+ and ClO- were determined to be 11 with Job plot and ESI-mass analysis. HPHN displayed low detection limits of 0.29 μM for Fe3+ and 0.77 μM for Fe