Kinetic Monte Carlo (KMC) is a powerful tool for studying catalytic reaction mechanisms. In this work, we present a practical approach for the mechanistic study of catalytic systems under site blocking deactivation through accelerated kinetic Monte Carlo (AKMC). It was used to simulate 31 elementary events proposed for graphene growth on copper, and subsequently validated by comparing graphene growth's time evolution from simulation with experiments. The AKMC reported in this study, which is capable of accelerating the time evolution of catalytic systems under evolving permanent blocking of active sites, advances the application of KMC for mechanistic studies of systems undergoing catalytic deactivation. Moreover, using this approach, new fundamental insights on the graphene growth mechanism was unveiled, highlighting the role of CH species rather than C adatoms in the growth of graphene. (C) 2019 Elsevier Inc. All rights reserved.