Thin films of alpha-Mn were epitaxially grown on the 4H-SiC (0 0 0 1) homoepitaxial substrates by using the molecular beam epitaxy. In situ reflection high-energy electron diffraction (RHEED), ex situ X-ray diffraction (XRD), atomic force microscopy (AFM) and the fluorescence extended X-ray absorption fine structure (EXAFS) are used to characterize their structural properties. We found that the a-Mn films with mirror-like appearance keep epitaxial growth on the 4H-SiC substrates despite of their very dissimilar nature of the crystal structure, bonding and chemical properties. The epitaxial relationship between body-centered-cubic (bcc) Mn and 4H-SiC is Mn (1 1 0)//4H-SiC(0 0 0 1) with Mn[0 0 1]//4H-SiC [1(1) over bar 00]. (c) 2006 Elsevier B.V. All rights reserved.