Multifunctional carbon-based materials exhibit a large number of unprecedented active sites via an electron transfer process and act as a desired platform for exploring high-performance electroactive material. Herein, we exemplify the holistic design of a heterometallic nanostructured material (MWCNTs@KR-6/Mn/Sn/Pb) formed by the integration of metals (Mn2+, Sn2+, and Pb2+) and a dipodal ligand (KR-6) at the surface of multiwalled carbon nanotubes (MWCNTs). First, MWCNTs@KR-6 was readily synthesized via a noncovalent approach, which was further sequentially doped by Mn2+, Sn2+, and Pb2+ to give MWCNTs@KR-6/Mn/Sn/Pb. The designed material showed excellent electrochemical activity for the discrimination of insecticides belonging to structurally different classes. In contrast to that of the individual building components, both the stability and electrochemical activity of heterometallic nanostructured material were remarkably enhanced, resulting in a magnificent electrochemical performance of the developed material. Hence, the current work reports a comprehensive synthetic approach for MWCNTs@KR-6/Mn/Sn/Pb synthesis by synergizing unique properties of the heterometallic complex with MWCNTs. This work also offers a new insight into the design of multifunctional carbon-based materials for discrimination of different analytes on the basis of their redox potential.