<p>Schiff base architectures and their transition metal complexes serve as specialized surface modifiers and recognition elements in electrochemical sensing. The core innovation of these architectures lies in the strategic flexibility of the azomethine (–C = N–) linkage, which provides a highly programmable coordination environment, ensuring enhanced sensitivity and selectivity across potentiometric, voltammetric, amperometric, and impedimetric platforms. However, critical research pain points and current operational limitations—such as short operational lifetimes and fabrication challenges—remain major bottlenecks. This review systematically evaluates these architectural constraints, delineating the specific advantages and limitations of each sensing modality. Furthermore, viable solutions derived from compiled literature are proposed to overcome these bottlenecks, outlining critical future perspectives for advancing the next generation of robust electrochemical sensors.</p>