Abstract
<jats:p>The characterization of biointerfaces where biological molecules interact with material surfaces remains a significant challenge due to their complex, dynamic, and heterogeneous nature. Conventional methods often fall short in capturing real-time molecular interactions and the subtle changes occurring at these interfaces. Electrochemical techniques provide a powerful solution, offering label-free, sensitive, and real-time analysis of biomolecular events at electrode surfaces. This chapter presents a comprehensive overview of electrochemical methods for investigating biointerfaces, which are essential in biosensor development, diagnostics, and biomedical research. Techniques such as cyclic voltammetry, electrochemical impedance spectroscopy, and in situ methods are explored in depth, alongside advanced systems like microfluidic–electrochemical platforms. The chapter also discusses how these techniques enable researchers to evaluate surface reactivity, biomolecule adsorption, and electrode stability, thereby facilitating the design of highly responsive and selective biosensors. Emerging technologies including wearable electrochemical sensors and 3D-printed biosensing interfaces are highlighted for their role in enhancing detection capabilities and broadening application areas. By addressing the limitations of conventional characterization approaches, electrochemical techniques significantly advance the sensitivity, specificity, and reliability of diagnostic tools.</jats:p>