Accurate simulation of the air–water interface of the overflowing sheet of water in weirs, referred to as nappe, is a challenging prospect from a computational fluid dynamics (CFD) modeling point of view. This study presents a systematic analysis of the widely used interface-capturing volume of fluid (VOF) technique for simulating nappe profiles, which has not received adequate attention in existing literature. Popular CFD codes employ the partial VOF (pVOF) method, which solves for a combined air–water flow and demarcates the free surface using an advection equation for the VOF function. The study finds that the coupled Reynolds-averaged Navier–Stokes (RANS)-pVOF model performs poorly in capturing non-aerated nappe flows. Moreover, the study shows that the choice of the turbulence closure model adopted has a negligible impact on the pVOF model outcome. Conversely, the study demonstrates that the original VOF approach, called TruVOF, which computes the flow only in the liquid regions, precisely simulates the nappe flow structure. The model performances are validated using the water level, velocity, and pressure distribution data from laboratory observations from a wide range of experiments conducted using weirs with square edged or rounded entrance. In addition, the study thoroughly examines the laminar modeling approach for simulating the nappe flow characteristics. This study demonstrates that the coupled laminar-TruVOF approach produces results that are at par with the RANS-TruVOF approach and presents a computationally inexpensive yet precise numerical tool for estimating the critical nappe flow characteristics and may be efficiently used to analyze the head-discharge characteristics of weirs.