A new crystallization process for sodium bicarbonate (NaHCO3) was studied, proposing the use of osmotic membrane distillation crystallization. Crystallization takes place due to the saturation of the feed solution after water evaporation on the feed side, permeating through the membrane pores to the osmotic side. The process operational parameters, i.e., feed and osmotic velocities, feed concentration, and temperature were studied to determine the optimal operating conditions. Regarding the feed and osmotic velocities, values of 0.038 and 0.0101 m/s, respectively, showed the highest transmembrane flux, i.e., 4.4 × 10−8 m3/m2·s. Moreover, study of the temperature variation illustrated that higher temperatures have a positive effect on the size and purity of the obtained crystals. The purity of the crystals obtained varied from 96.4 to 100% In addition, the flux changed from 2 × 10−8 to 7 × 10−8 m3/m2·s with an increase in temperature from 15 to 40 °C. However, due to heat exchange between the feed and the osmotic solutions, the energy loss in osmotic membrane distillation crystallization is higher at higher temperatures.