In this work, we introduced a simple aggregation-induced emission enhancement (AIEE) sensor (PHCS) which can selectively detect and discriminate three environmentally and biologically imperative heavy metal ions (Cu2+, Co2+ and Hg2+) and a hazard class 1 categorized nitro-explosive picric acid (PA) in differential media. By virtue of its weak fluorescence attributes in pure organic medium owing to the synergistic operation of multiple photophysical quenching mechanisms, the molecular probe showcased highly selective 'TURN ON' fluorogenic response towards hazardous Hg2+ with a limit of detection (LOD) as low as 97nM. Comprehensive investigation of binding mechanism throws light on the cumulative effect of probe-metal complexation induced chelation enhanced fluorescence (CHEF) effect and subsequent AIEE activation within the formed probe-metal adducts. Noteworthily, the probe (PHCS) can be readily used in real water samples for the quantitative determination of Hg2+ in a wide concentration range. In addition, the probe displayed modest colorimetric recognition performances to selectively detect and discriminate two essential heavy metal ions (Cu2+ and Co2+) with a LOD of 96nM and 65nM for Cu2+ and Co2+ respectively, in semi-aqueous medium. Intriguingly, based on high photoluminescence efficiency, the AIEE active nano-aggregated PHCS displayed a remarkable propensity to be used as a selective and ultra-sensitive 'TURN-OFF' fluorogenic chemosensor towards PA with LOD of 34.4ppb in aqueous medium. Finally, we specifically shed light on the interaction of PHCS hydrosol towards PA using some unprecedented techniques, which helped uncover new photophysical insights of probe-explosive molecule interaction.