The presence of pesticides, pharmaceuticals, heavy metals, and other contaminants in environmental matrices is a growing global concern. One of the primary challenges in detecting environmental pollutants at trace levels is achieving high sensitivity and selectivity in complex matrices such as contaminated soil and water. Therefore, in-situ sensing and quantifying these compounds is crucial for assessing contamination severity at its source. Vertically aligned nanostructures (VANs) on the functioning electrode’s surface offer a promising solution for monitoring pollutants due to their tailored surface properties, including high surface area (increase more attachment sites for the electroactive species), increased surface roughness (expand more nucleation sites), fast charge transfer kinetics (electron transfer inside and/or outside from nanostructure surface to electrolyte), and high stability. However, conventional methods for fabricating VANs involve many environmentally aggressive chemicals. Consequently, there is a growing concern about developing nature-inspired VANs using phytochemicals derived from plants and their organs for efficient sensing of environmental pollutants. This review comprehensively discusses the synthesis of powder and VANs using conventional and nature-inspired methods and explores the pivotal role of nanostructures in enhancing the sensing performance of sensors. This report also documents the comparison of immobilized (using binder) and VANs onto working electrode-based sensors for detecting environmental pollutants. The main focus of this review is on the nature-inspired development of VANs based miniaturized three-electrode system device for on-site and real-time monitoring of environmental pollutants with high stability and reusability.