Electroactive materials and their applications are enjoying renewed attention, in no small part motivated by the advent of nanoscale tools for their preparation and study. While the fundamentals of charge and mass transport in electrolytes on this scale are by and large well understood, their interplay can have subtle manifestations in the more complex situations typical of, for example, integrated microfluidics-based applications. In particular, the role of faradaic processes is often overlooked or, at best, purposefully suppressed via experimental design. In this introductory article we discuss, using simple illustrations from our laboratories, some of the manifestations of electrochemistry in electroactive materials.