This paper presents the experimental results of liquid-liquid microflows in a coaxial microfluidic device with mass transfer. Three working systems were n-butanol + phosphoric acid (PA) + water, methyl isobutyl ketone (MIBK) + PA + water, 30% kerosene in tri-n-butylphosphate (TBP) + PA + water. The direction and intensity of mass transfer were adjusted by adding PA in one of two phases mutual saturated in advance. When PA transferred from the organic phase to the aqueous phase, tiny aqueous droplets may generate inside the organic phase by mass transfer inducement to form a new W/O/W flow pattern directly on some special cases. Once the PA concentration was very high, violent Marangoni effect could be observed to throw part of organic phase out of droplets as tail. The interphase transfer of PA could expand the jetting flow region, in particular for systems with low or medium interfacial tension and when the mass transfer direction was from the aqueous phase to the organic phase.