This study investigates the turbulent two‐phase dispersion of toluene‐water in micro‐impinging jet (MIJ) mixers using both experimental and numerical methods. We employ computational fluid dynamics combined with the population balance model (CFD‐PBM) to predict the mean droplet size (d32) and droplet size distribution (DSD). The numerical predictions align well with the experimental results. The liquid–liquid dispersion in the MIJ mixer is a two‐step process, each step governed by the velocity ratio (r) and Reynolds number (Rej), respectively. By increasing the volume flow rate (Q) and r, or by reducing the diameter of the outlet orifice of mixing chamber (Do), the dispersion process can be intensified. This leads to the production of smaller droplets with a narrow DSD within a millisecond timeframe. Additionally, we propose a correlation for d32 that accurately describes the two‐step dispersion process of the mixer, providing a reliable guide for the design and optimization of liquid–liquid systems.