In the extraction method for preparing KH2PO4, one of the key processes is the selective extraction of HCl over H3PO4. In our work, extraction kinetic studies have been carried out in a microfluidic device with a coaxial microchannel, using the extractant of 33.3% (by volume) trioctylamine (TOA) dissolved in n-octanol, with different aqueous phases: the HCl solution, the H3PO4 solution, and H3PO4 and KCl solutions of different concentrations. The changes of the extraction efficiency of HCl and H3PO4 and the selectivity for HCl along with the residence time were investigated. We found that fast extraction kinetics could be realized in microfluidic devices, and that HCl could be extracted faster than H3PO4 due to smaller mass transfer resistance and much stronger reaction between HCl and TOA. For the extraction of H3PO4 and KCl solutions, the selectivity for HCl first increased and then decreased when TOA was in excess of H3PO4 in the initial feeds, and in contrast, always increased when H3PO4 was in excess of TOA in the initial feeds. The diverse changes of selectivity for HCl along with the residence time indicate that a dynamic control of selectivity in microfluidic devices may be important and accessible for improving the KH2PO4 conversion efficiency in extraction method. (C) 2015 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.