A new mechanistic model for the evaluation of mass transfer performance in columns equipped with structured packings is proposed. The model is developed by taking into account the interactions of falling film with the gas phase, and thus, it includes the effects of both the physical properties of the working fluids and the geometrical characteristics of the packings. The model does not introduce any adjustable parameter but relies on the semiempirical equations developed earlier for the prediction of the pressure drop and the mass transfer coefficients in absorption processes. The model has been validated using experimental data obtained under total reflux conditions with different systems at different operating conditions, including the conventional and high capacity packings of different specific surface areas and different corrugation angles. The results indicated that simple mechanistic models can be used with confidence to describe the fluid dynamics within the packings. The adoption of the present model is suggested for systems for which experimental data are not available, while for experimentally tested systems, higher prediction accuracy could be obtained using different models, based on a larger number of adjustable parameters that have to be tuned on the experimental data. The knowledge of the liquid film hydrodynamic behavior can also allow understanding of the reasons for some observed deviations in performance such as the efficiency "hump" occurring at specific operating conditions in distillation columns.