The interfacial area between two phases plays a crucial role in the mass transfer rate of gas–liquid processes such as absorption. In this context, the droplet size distribution within the flow field of a droplet-based absorber significantly affects the surface area, thereby influencing the absorption efficiency. This study focuses on developing a computational fluid dynamics (CFD) model to predict the size and distribution of water droplets free-falling in a transparent square tube. This model serves as a digital twin of our experimental setup, enabling a comparative analysis of experimental and computational results. For the accurate measurement of droplet size and distribution, specialized experimental equipment was developed, and a high-speed camera along with Fiji software was used for the capturing and processing of droplet images. At the point of injection and at two different heights, the sizes and distributions of falling droplets were measured using this setup. The interaction between the liquid water droplets and the gas phase within the square tube was modeled using the Eulerian–Lagrangian (E-L) framework in the STAR-CCM+ software. The E-L multiphase CFD model yielded approximations with errors ranging from 11 to 27% for various average mean diameters, including d10, d20, d30, and d32, of the liquid droplets at two distinct heights (200 mm and 400 mm) for both nozzle plates. This comprehensive approach provides valuable insights into the dynamics of droplet-based absorption processes.