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Graphical abstract Abstract The mixing of binary droplets is of paramount importance in microfluidic systems. In order to reveal the mixing mechanism of two free droplets suspended in the immiscible phase, we have developed a novel experimental setup to study the internal mixing in coalescing droplets with varying interfacial tension differences and droplet sizes. It is confirmed that the interfacial energy of droplets supports the jet flow and liquid bridge expansion during the coalescence of droplets. The increase of interfacial tension difference can increase the intensity of jet flow accompanied with slower liquid bridge expansion, which enhances the mixing of droplets. The decrease of droplet size can increase the initial velocity of jet flow. However, the intensity of jet flow decreases due to the rapid expansion of the liquid bridge, which results in weaker internal mixing. On this basis, a Reynolds number incorporating the jet velocity and droplet size is proposed to characterize the vortex size, which represents the degree of droplet mixing. This study presents an effective approach for enhancing the mixing of droplets. [ABSTRACT FROM AUTHOR]