Performance of six different microbial fuel cells (MFCs) made from baked clayware, having 450 ml effective anodic chamber volume, was evaluated, with different configurations of separator electrode assemblies, to study the feasibility of bioelectricity generation and high-strength wastewater treatment in a single-chambered mediator-less air-cathode MFC. Superior performance of an air-cathode MFC (ACMFC) with carbon coating on both sides of the separator was observed over an aqueous cathode MFC, resulting in a maximum volumetric power of 4.38 W m−3 and chemical oxygen demand (COD) removal efficiency of more than 90 % in a batch cycle of 4 days. Hydrophilic polymer polyvinyl alcohol (PVA) was successfully used as a binder. The problem of salt deposition and fouling of cathode could be minimized by using a sock net current collector, replacing the usual stainless steel wire. However, electrolyte loss due to evaporation is a problem that needs to be resolved for better performance of an ACMFC.