The liquid-liquid flow pattern and extraction mass transfer kinetics for V(V) were investigated in microchannels using primary amine N1923 extractant. 15vol% N1923 was used as the continuous phase and V(V) aqueous solution as the dispersed phase. The flow patterns of two immiscibility phases at different flow rates and the effects of residence time and microchannel diameter on mass transfer as a function of flow rate were studied. The study found that compared to 1:1, with the increase of the two-phase flow velocity, the slug flow length and the specific interface area remained unchanged, and two phase fluid by Raydrop microchannel flowed into the external capillary microchannel because of the expansion of microchannel changed the way of two-phase flow, made the same experimental conditions at the same time appeared a variety of flow pattern in the microchannel. At the same time the two-phase flow velocity was positively correlated with the total mass transfer coefficient, it showed that the influence of flow pattern on mass transfer can be ignored in this research system. In addition, the residence time was negatively correlated with the total mass transfer coefficient in the same channel, which indicated that significant mass transfer occurred at the entrance of the two-phase contact channel, and the mass transfer rate was the highest at this time. After the diameter of the external capillary microchannel was changed, the mass transfer effect of 254 μm tube diameter was 9 times that of 750 μm tube diameter at the same mixing rate, which indicated that the inner circulation strength and specific interface area of small tube diameter were more significant. Finally, the experimental results of the total volume mass transfer coefficient were correlated with the empirical formula of the total volume mass transfer coefficient, which provided a theoretical basis for the realization of green metallurgical technology of microchannel amplification.