Thin films of Bi2VO5.5 (BVO) were prepared on polycrystalline yttria-stabilized zirconia (YSZ) and single-crystal SrTiO3 [STO] (100) and (110) substrates by a coating-pyrolysis process. X-ray diffraction (XRD) θ-2θ scans showed that the crystallinity of the films increased with increasing heat-treatment temperature. The crystallinity of the BVO (001) films was so high that the XRD peak intensity of the 002 reflection was comparable with that of the STO 100 reflection. XRD pole-figure analysis and reciprocal-space mapping revealed that the films on YSZ are uniaxially c-axis oriented, while epitaxial BVO films with the (001) orientation have grown on STO (100). On the other hand, the occurrence of epitaxial (114) orientation in the BVO films was discovered by the present study and is similar to the case of (116)-oriented SrBi2Ta2O9 films on STO (110).