In this work, we investigated the orientation and the polarization of ZnO nanoparticles, which serve as building blocks of highly monodisperse microspheres, using a droplet microfluidic-assisted synthesis method. We observe, for the first time, a square lattice organization of liquid microdroplets, in a steady state, at the oil/water interface. Such square organization reveals clearly a dipolar organization of ZnO nanoparticles at the surfaces of droplets at the early stage of ZnO nanocrystal aggregation and microsphere formation. We discuss different models of organization of ZnO nanoparticles and show that the well-known tip-streaming effect in droplets in microfluidics explains the reason for the obtained dipolar droplets. The square organization is illustrated and explained.