Metal-organic frameworks (MOFs) have attracted considerable attention as novel nanoporous materials that combine the properties of organic and inorganic porous materials. HKUST-1 is one of the most well-developed and representative MOFs with wide applications in gas storage and separation, adsorption, and capture. In this study, we used microfluidics, an advanced technique of manipulation of small fluid volumes in microscale or even nanoscale channels, to investigate the effect of sodium dodecyl sulfate (SDS) on the growth of HKUST-1 crystals. We directly observed the morphological evolution of HKUST-1 crystals through droplet arrays with the SDS concentration gradient. The morphology of HKUST-1 evolved from cubic to cuboctahedron and finally to octahedron with increasing SDS concentration. The study results demonstrated the important role played by anions in solution in the structural regulation of HKUST-1.