In this paper, we present experimental results on how minute droplets are formed on fiber optic end faces. Results show that reproducible picoliter volumes can be generated when fibers are retracted from an aqueous phase contained under an inert fluorinated immiscible liquid, with a coefficient of variation (CV) of 0.7-2.3%. The droplet formation was analyzed as a function of the fiber diameter, retraction speed, and wettability. Experiments reveal a volume-determining critical equilibrium contact angle between 60 and 75, defining the onset of fiber end-face dewetting. The dynamics of the droplet snap-off progression was characterized using high-speed imaging in order to explain the observed wettability-volume dependency.