Direct contact membrane distillation (DCMD) process using polyvinylidene fluoride (PVDF) membrane was used for fluoride removal from aqueous solution. This study has been carried out on heat and mass transfer analyses in DCMD. The dusty-gas model was used to analyze the mass transfer mechanism and to calculate the permeate flux. The heat transfer is analyzed based on energy balance, and the different layers are considered as a series of thermal resistances. Mass transfer analysis showed that the transition Knudsen-molecular diffusion is the dominant mechanism to describe the transport of water vapor through the pores of the PVDF membrane. The most significant operating parameter is the feed temperature. The permeate increases sensitively with feed temperature and velocity, and it shows insignificant change with feed salts concentration. Heat transfer analysis showed the conduction through the matrix of the membrane presents the major part of available energy. The increasing feed temperature leads to increase thermal efficiency (TE) and decrease temperature polarization coefficient (TPC). The experimental results are in good agreement with theoretical values. Therefore, it is suggested to work at high feed temperature, which will benefit both the thermal efficiency and permeate flux. The experimental results proved that DCMD process is able to produce almost fluoride-free water suitable for many beneficial uses.