The present work investigates the performance in terms of recovery of pure water and NaCl crystals from concentrated brine with the help of membrane distillation-crystallization (MDC). The flat-sheet polyvinylidene fluoride membranes were prepared by phase inversion method and modified with additives lithium chloride (LiCl) and acetone. Membrane properties such as contact angle, porosity, pore size, thickness, surface morphology, etc. were characterized by using different methods. The effects of membrane modification and different operating parameters on the performance of MDC were studied. Significant improvements in fluxes were obtained in the case of modified membranes showing a great potential toward MDC process.