Algae biocathodes have become one of the most sustainable replacements for abiotic cathodes which were expensive and had toxic chemical oxidant by-products. In this study, a pure culture of Chlorella vulgaris from a photobioreactor was pumped into a photosynthetic microbial desalination cell to treat real landfill leachate (had undergone physical treatment) under varying ‘factor-conditions (FC)’ to embark on a factor-performance relation (FPR) study. This aimed at determining the relationship between operating factors and to depict the most favourable conditions (and range) in order to boost the overall performance of the reactor/cell. Three groups of FC (A, B and C) were adapted, in that, under FC A external resistance was varied, FC B varied pumping rate and FC C varied temperature, light intensity and dissolved oxygen under conditions flow and recirculation mode. Results showed 95% chemical oxygen demand (COD) removal, a maximum power density of 121.57 mWm−2 (anodic volume) and an average desalination rate of 3.93 mg/L/h. The varying results at different FC showed the significant impact of operating conditions on performance. Algae biocathodes also proved to be an essential benefit in boosting the sustainable application of microbial desalination cells (MDCs) in wastewater and landfill pre-treatment as well as the generation of bioenergy.