The microstructure and orientation relationships of epitaxial (111)-oriented SrTiO3 thin films grown by radio frequency magnetron sputtering on epitaxial (111)-oriented Pt/Ti electrodes on sapphire were investigated using x-ray diffraction, conventional and scanning transmission electron microscopy. We show that the epitaxial growth of (111)-oriented SrTiO3 films was promoted by thin Ti adhesion layers underneath the Pt electrode. The SrTiO3 films nucleated with two twin-related orientation variants, rotated by 180° about the 〈111〉 surface normal. The twin boundaries were oriented approximately normal to the film plane, but no strong preference for a specific boundary plane was observed. Growth mechanisms and the relationships to the dielectric properties are discussed.