Recent investigations have utilized the measurement of the critical angle for reflection from a liquid‐solid interface for determination of the elastic constants of the solid. For anisotropic media, this technique is appropriate only for certain special cases of the incident plane and reflecting surface. We discuss here the general condition for the critical angel in anisotropic media and show that for some planes in quartz, major errors may arise if one employs the usual statement of Snell’s law for definition of the critical angle.Subject Classification: [43]20.30; [43]35.26.