For several decades, evaporation phenomena have been intensively investigated for a broad range of applications. However, the dynamics of contact line depinning during droplet evaporation has only been inductively inferred on the basis of experimental data and remains unclear. This study focuses on the dynamics of contact line depinning during droplet evaporation based on thermodynamics. Considering the decrease in the Gibbs free energy of a system with different evaporation modes, a theoretical model was developed to estimate the receding contact angle during contact line depinning as a function of surface conditions. Comparison of experimentally measured and theoretically modeled receding contact angles indicated that the dynamics of contact line depinning during droplet evaporation was caused by the most favorable thermodynamic process encountered during constant contact radius (CCR mode) and constant contact angle (CCA mode) evaporation to rapidly reach an equilibrium state during droplet evaporation.