A hollow fiber vacuum membrane distillation (VMD) module was modeled using finite element analysis, and the results were used to conduct an exergy efficiency analysis for a solar-thermal desalination scheme. The performance of the VMD module was simulated under various operating conditions and membrane parameters. Membrane porosity, tortuosity, pore diameter, thickness, and fiber length were varied, along with feed temperature and feed configuration. In all cases, polarization phenomena were seen to inhibit the performance of the module. Under VMD operation, polarization of salt concentration was seen to be the main determining factor in the reduction of permeate flux. Within the boundary layer, salt concentration was seen to rapidly increase from the feed mass fraction of 0.035 to the saturation point. The increase in salt concentration led to a decrease in saturation pressure, the driving force for separation. Charging the feed into the shell instead of the lumen side of the membranes resulted in a further decrease in permeate flux. It is shown that adding a baffling scheme to the surface of the fibers can effectively reduce polarization phenomena and improve permeate flux. Increasing the overall recovery ratio was seen to increase the exergy efficiency of the system. Exergy efficiency was seen to have almost no dependency on membrane parameters due to the low recovery ratio in a single pass and the high heating duty required to reach the desired temperature for the feed stream.