A facile method has been developed for fabricating selective and sensitive electrochemical sensors for the detection of toxic metal ions, which invokes incorporation of palladium nanoparticles (Pd NPs) on porous activated carbons (PACs). The PACs, which were derived from waste biomass feedstock (fruit peels), possess desirable textural properties and porosities favorable for dispersion of Pd NPs (ca. 3-4 nm) on the graphitic PAC substrate. The Pd/PAC composite materials so fabricated were characterized by a variety of different techniques, such as X-ray diffraction, field-emission transmission electron microscopy, gas physisorption/chemisorption, thermogravimetric analysis, and Raman, Fourier-transform infrared, and X-ray photon spectroscopies. The Pd/PAC-modified glassy carbon electrodes (GCEs) were exploited as electrochemical sensors for the detection of toxic heavy metal ions, viz., Cd(2+), Pb(2+), Cu(2+), and Hg(2+), which showed superior performances for both individual as well as simultaneous detections. For simultaneous detection of Cd(2+), Pb(2+), Cu(2+), and Hg(2+), a linear response in the ion concentration range of 0.5-5.5, 0.5-8.9, 0.5-5.0, and 0.24-7.5 μM, with sensitivity of 66.7, 53.8, 41.1, and 50.3 μA μM(-1) cm(-2), and detection limit of 41, 50, 66, and 54 nM, respectively, was observed. Moreover, the Pd/PAC-modified GCEs also show perspective applications in detection of metal ions in real samples, as illustrated in this study for a milk sample.