The theory of the kinetics of metastable pit nucleation in terms of the Point Defect Model (PDM) has been applied the first time to describing the evolution of the nucleation rate of metastable pits on a variety of metallic substrates. The PDM successfully accounts for the experimental data that have been reported in the literature on stainless steel, carbon steel, iron, aluminum, and Alloy-22, and which are judged to be reliable and reproducible. Important fundamental parameters related to metastable pitting such as total number density of pitting nucleation sites, dissolution time of the cap over the pit, energy related to absorption of the aggressive ions into oxygen vacancies in the surface of the barrier layer, vacancy condensation rate, and the time at which the nucleation rate of metastable pits is maximum were obtained from the optimization of the PDM on the experimental data, as reported in the present paper. The values obtained for those parameters are in good agreement with values and observations reported elsewhere. The present work successfully demonstrates the capacity of the PDM in accounting for experimental observations of metastable pitting and that the PDM can be applied as an underlying theory for studying and understanding metastable pitting on metal surfaces. (C) 2016 The Electrochemical Society. All rights reserved.