Multi-Effect Distillation (MED) is a suitable solution for water desalination and brine concentration in a wide scale of applications. Its potential is even more relevant when they are powered by a variable energy source owing to its operational flexibility. This study introduces a comprehensive methodology for assessing the performance of MED processes, encompassing crucial aspects such as system configuration, instrumentation requirements, test procedure and evaluation criteria like performance metrics adequacy and uncertainty determination. The proposed methodology has been successfully implemented and validated at an experimental MED facility located at the Plataforma Solar de Almería (PSA, Spain). Through this research, valuable insights and guidelines are provided to achieve an accurate performance evaluation of MED systems in practical settings.