The effect of compositing multiwalled carbon nanotubes (MWCNTs) with polystyrene (PS) to fabricate nanofibrous membrane by electrospinning technique and comparing the direct contact membrane distillation (DCMD) performance of the blank and composite membranes is evaluated numerically. Surface morphology of both the pristine and the composite membrane was studied by SEM imaging while the average fiber diameter and average pore size were measured using ImageJ software. Static water contact angle and porosities were also determined for both membranes. Results showed significant enhancement in both the hydrophobicity and porosity of the composite membrane by increasing the static water contact angle from 145.4° for the pristine PS membrane to 155° for the PS/MWCNTs composite membrane while the porosity was increased by 28%. Simulation results showed that at any given feed inlet temperature, the PS/MWCNTs membrane have higher permeate flux and better overall system performance.