Biofuel cells (BFCs) are an environmental friendly technology that can simultaneously perform wastewater treatment and generate electricity. Peculiarities that hinder the widespread introduction of this technology are the need to use artificial aeration and chemical catalysts, which make the technology expensive and cause secondary pollution. A possible solution to this issue is the use of biocathodes with microalgae and cyanobacteria. Microalgae in the biocathodic chamber produce oxygen as the terminal electron acceptor. Various BFC technologies with algal biocathode (microbial fuel cells, microbial desalination cells, and plant microbial fuel cells) can address a variety of issues such as wastewater treatment, desalination, and CO2 capture. The main technological parameters that influence the performance of the biocathode are light, pH, and temperature. These technological parameters affect photosynthetic production of oxygen and organic compounds by microalgae or cyanobacteria, and hence affect the efficiency of electricity production, wastewater treatment and production of added-value compounds in microalgae biomass like lutein, violaxanthin, astaxanthin. The ability to remove carbon, nitrogen, and phosphorus compounds; antibiotics; and heavy metals by pure cultures of microalgae and cyanobacteria and by mixed cultures with bacteria in the cathode chamber can be used for wastewater treatment.