The flow of thin falling liquid films is unstable to long-wave disturbances. The flow instability leads to development of waves at the liquid–gas interface. The effect of the waves on heat and mass transfer in falling liquid films is a subject of ongoing scientific discussion. In this work, numerical investigation of the wave dynamics has been performed using a modified volume-of-fluid (VOF) method for tracking the free surface. The surface tension is described using the continuum surface force (CSF) model. With low disturbance frequency, solitary waves of large amplitude are developed, which are preceded by low-amplitude capillary waves. With high disturbance frequency, low amplitude sinusoidal waves are developed. The waveforms dependent on the Reynolds number and disturbance frequency are summarized in a form of a regime map. A correlation describing the separation curve between the sinusoidal waves regime and solitary waves regime is proposed. The wave parameters (peak height, length, and propagation speed) are computed from the simulation results and compared with available experimental correlations in a wide range of parameters. The effects of the disturbance frequency and the plane inclination angle on the wave dynamics have been studied. The interaction of waves initiated by simultaneous disturbances of two different frequencies has been investigated. The heat transfer in the wavy film has been simulated for the constant wall temperature boundary condition. The effects of Prandtl number and disturbance frequency on local and global heat transfer parameters have been investigated. It has been shown that the influence of waves on heat transfer is significant for large Prandtl numbers in a specific range of disturbance frequencies.