The over-exploitation of fossil fuels and their negative environmental impacts have attracted the attention of researchers worldwide, and efforts have been made to propose alternatives for the production of sustainable and clean energy. One proposed alternative is the implementation of bioelectrochemical systems (BESs), such as microbial fuel cells (MFCs), which are sustainable and environmentally friendly. MFCs are devices that use bacterial activity to break down organic matter while generating sustainable electricity. Furthermore, MFCs can produce bioelectricity from various substrates, including domestic wastewater (DWW), municipal wastewater (MWW), and potato and fruit wastes, reducing environmental contamination and decreasing energy consumption and treatment costs. This review focuses on recent advancements regarding the design, configuration, and operation mode of MFCs, as well as their capacity to produce bioelectricity (e.g., 2203 mW/m2) and fuels (i.e., H2: 438.7 mg/L and CH4: 358.7 mg/L). Furthermore, this review highlights practical applications, challenges, and the life-cycle assessment (LCA) of MFCs. Despite the promising biotechnological development of MFCs, great efforts should be made to implement them in a real-time and commercially viable manner.