Microbial fuel cells and their related microfluidic systems have emerged as promising greener energy alternatives for the exploitation of avenues related to combined power and wastewater treatment operations. Moreover, the potential for their application in biosensing technology is large. However, while the fundamental principles of science that govern the design and operation of microbial fuel cells (MFCs) and microfluidic microbial fuel cells (MMFCs) are similar to those found in colloid science, the literature shows that current research lacks sufficient reference to the electrostatic and electrokinetic aspects, focusing mostly on aspects related to the architecture, design, anodes, microbial growth and metabolism, and electron transfer mechanisms. In this regard, research is yet to consider MFCs and MMFCs in the context of electrostatic and electrokinetic aspects. In this extensive review, we show, for the first time, the interrelationship of MFCs and MMFCs with electric double layer theory. Consequently, we show how the analytical solution to the mean field Poisson–Boltzmann theory relates to these systems. Moreover, we show the interrelationship between MFC and MMFCs’ performance and the electric double layer and the associated electrostatic and electrokinetic phenomena. This extensive review will likely motivate research in this direction.