Conducting Polymers for Electrochemical Sensing: From Materials and Metrology to Intelligent and Sustainable Biointerfaces

Conducting polymers (CPs) have become cornerstone materials in electrochemical sensors and biosensors due to their mixed ionic–electronic conduction, mechanical softness, and intrinsic biointerface compatibility. This review provides a comprehensive and critical overview of the field, tracing the evolution of CP-based devices from classical poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), polyaniline (PANI), and polypyrrole (PPy) electrodes to emerging nanostructured, hybrid, wearable, and transient systems. We discuss fundamental charge-transport mechanisms, doping strategies, structure–property relationships, and the role of morphology and biofunctionalization in dictating sensitivity, selectivity, and stability. Particular emphasis is placed on reliability challenges—including drift, dopant leaching, environmental degradation, and biofouling—and on the current lack of standardized metrology, which hampers cross-study comparability. We propose a framework for rigorous calibration, reference electrode design, and data reporting, enabling quantitative benchmarking across materials and architectures. To support meaningful cross-platform comparison, representative performance envelopes—including conductivity, limit of detection, sensitivity, selectivity strategies, and operational stability—are critically benchmarked across major CP families and sensing modalities. Finally, we explore future directions such as organic mixed ionic–electronic conductors, biohybrid and living polymer interfaces, Artificial Intelligence-driven modeling, and sustainable transient electronics.