The application of extractants in whole-cell biocatalysis can have a positive impact on industrial fermentations, in terms of productivity, total amount of product produced, and cell growth. When a product is continuously removed from the microorganism surroundings, product inhibition will be diminished. The strategy is exemplified using phenol as the product and the extractant is selected for solvent-impregnated resins, which can prevent emulsification problems that are commonly encountered in in situ extractive recovery of fermentation products. A systematic approach for selection of superior extractants in whole-cell biocatalysis is discussed in this paper. Three criteria are taken into account, namely, extractant toxicity (log P-o/w values), product selectivity, and extractant regeneration.