Fluorous molecules partition out of an organic phase and into a fluorous (highly fluorinated) phase in a liquid-liquid extraction. New fluorous techniques allow simple yet substantive separations of organic reaction mixtures based on the presence or absence of a fluorous tag. Fluorous-tagged molecules can also be separated from nontagged molecules by solid phase extraction over fluorous reverse-phase silica gel. This technique is ideal for solution-phase parallel synthesis because it allows simple yet substantive separations of organic reaction mixtures.