Ferroelectric domain formation is an essential feature in ferroelectric thin films. These domains and domain walls can be manipulated depending on the growth conditions. In rhombohedral BiFeO 3 thin films, the ordering of the domains and the presence of specific types of domain walls play a crucial role in attaining unique ferroelectric and magnetic properties. In this study, controlled ordering of domains in BiFeO 3 film is presented, as well as a controlled selectivity between two types of domain walls is presented, i.e., 71° and 109°, by modifying the substrate termination. The experiments on two different substrates, namely SrTiO 3 and TbScO 3 , strongly indicate that the domain selectivity is determined by the growth kinetics of the initial BiFeO 3 layers.