Characterization of the vacuum ultraviolet (VUV) reflectance of silicon photomultipliers (SiPMs) is important for large-scale SiPM-based photodetector systems. We report the angular dependence of the specular reflectance in a vacuum of SiPMs manufactured by Fondazionc Bruno Kessler (FBK) and Hamamatsu Photonics K.K. (HPK) over wavelengths ranging from 120 nm to 280 nm. Refractive index and extinction coefficient of the thin silicon-dioxide film deposited on the surface of the FBK SiPMs are derived from reflectance data of a FBK silicon wafer with the same deposited oxide film as SiPMs. The diffuse reflectance of SiPMs is also measured at 193 nm. We use the VUV spectral dependence of the optical constants to predict the reflectance of the FBK silicon wafer and FBK SiPMs in liquid xenon.