Boron phosphide (BP) is a material of interest for development of a high-efficiency solid-state thermal neutron detector. For a thick film-based device, microstructure evolution is key to the engineering of material synthesis. Here, we report epitaxial BP films grown on silicon carbide with vicinal steps and provide a detailed analysis of the microstructure evolution and strain relief. The BP film is epitaxial in the near-interface region but deviates from epitaxial growth as the film develops. Defects such as coherent and incoherent twin boundaries, dislocation loops, stacking faults concentrate in the near-interface region and segment this region into small domains. The formation of defects in this region do not fully release the strain originated from the lattice mismatch. Large grains emerge above the near-interface region and grain boundaries become the main defects in the upper part of the BP film. (C) 2014 Elsevier B.V. All rights reserved.