For concentrated photovoltaics (CPV), most of incident solar energy is wasted as heat. If the heat is not removed in time, the junction temperature of CPV will rise and eventually worsen the performance. To remove and harvest the waste heat, a direct contact membrane distillation (DCMD) is coupled to CPV for fresh water generation in this study. Based on the first and second laws of thermodynamics, key performance indicators for each component within the coupled system and the whole coupled system are derived. The basic performance features of the coupled system are revealed. The utmost power density, utmost energy efficiency and utmost exergy efficiency of the coupled system allow to be, 35.37%, 35.37% and 5.37% greater than that of single CPV, respectively. After optimizing electric current of CPV, the effects of solar irradiance, operating temperature of CPV, temperature and flow velocity of feed and permeate sides and thickness of membrane on the coupled system performance are studied via extensive parametric studies. In addition, monthly average performance of the proposed coupled system from January to October in 2021 in Ningbo, China is investigated. The results acquired may be beneficial to design and run such a real CPV-DCMD coupled system.