Incompetent governance of post-harvest horticultural crops especially apples and pears lead to numerous physiological storage disorders. In order to manage this issue, diphenylamine (DPA) is widely used as an antioxidant and anti-scald agent to preserve fruits from superficial scalds and degradation during storage. As a result, this research focuses on utilizing disposable electrodes constructed with sphere-shaped iron-manganese layered double hydroxide (FeMn-LDH) entrapped tungsten carbide (WC) nanocomposite on its electrochemical performances towards emergent food contaminant, DPA. The importance of the current work is the selection and design of hierarchically structured functional materials especially layered double hydroxides, in virtue of their outstanding properties. These multi-dimensional structures when introduced to form a composite with the highly beneficial tungsten carbide offer excellent characteristics such as exceptional accessibility to active sites, enhanced surface area, and high mass transport and diffusion which serves as advantageous for the electrochemical quantification of DPA. Furthermore, the synergy between FeMn-LDH and WC nanomaterials contributes to the higher active surface area, increased electrical conductivity, fast electron transportation, and ion diffusion, resulting in static properties including a wide linear range (0.01–183.34 μM), low detection limit (1.1 nM), greater sensitivity, selectivity, and reproducibility thus confirming the potential capability of the WC@FeMn-LDH sensor towards the interference-free determination of DPA which validates its practicality and feasibility in real-time. Hence, this work aims to stimulate the fabrication of various advanced hierarchical structures by a simple hydrothermal approach that can have veracity of potential applications.