When examining multiphase systems, primarily ones with liquid|liquid and liquid|gas interfaces, many interesting physicochemical phenomena such as reaction rate acceleration and surprising reaction pathways are present. To probe these chemistries, Multiphase Electrochemiluminescence Microscopy can be used to visualize both the statics and dynamics of these systems. Here, we will describe the progress of the field from its beginning, before the inclusion of microscopy, to current advancements. Furthermore, how multiphase ECL microscopy has elucidated exciting physicochemical phenomena will be discussed. Finally, we will look toward the future to examine research gaps in this field.