High-sensitivity charge coupled-device (CCD) cameras, efficient fibre optic bundles, high stable light source and 3D printing technologies now open large possibilities to probe redox species in solution and on confined surface by real-time absorption spectroelectrochemistry. This short review aims at providing an overview of the first work of absorption spectroelectrochemistry on redox-responsive self-assembled
monolayers (SAMs). Some practical aspects are emphasized to not underestimate the difficulties involved in set-up such instrumentation.