Water-in-oil (W/O) fermentation technology has the potential for overcoming the problems related with high broth viscosity in xanthan fermentations. By dispersing the aqueous broth in a continuous organic phase, the broth-thickening mechanisms are confined within the aqueous droplets without significantly increasing the overall viscosity. In this study, xanthan fermentations were made with perfluorocarbon (PFC) or vegetable oil as the organic phase. The results were compared with those obtained previously using n-hexadecane as the organic phase, to evaluate the effects of various properties. PFC provided easy phase separation at the end of fermentation but required higher power input for agitation, a direct result of its high density. The aqueous droplets formed were large (400–450 μm), limiting the cell concentration employable due to the occurrence of oxygen starvation in the inner core. One main advantage of using vegetable oil was its low cost. In addition, vegetable oil provided much finer droplets (<120 μm) and produced high xanthan concentrations (>100 g l−1). However, complete phase separation for product recovery was difficult to achieve. Fermentations in both organic phases were terminated by the occurrence of phase inversion to highly viscous O/W dispersions at aqueous-phase volume fractions of 0.53–0.56. The initial fraction was 0.3 but changed due to base addition for pH adjustment and nutrient addition for prolonged production.