I review polarimetric observations of presumably single, hot, luminous stars. The stellar types discussed are OB stars, B[e] supergiants, Luminous Blue Variables (LBV), Wolf-Rayet (W-R) stars, and type II supernovae (SN). It is shown that variable, intrinsic polarization is a common phenomenon in that part of the Hertzsprung-Russell (HR) diagram which these stars occupy. However, much observational work remains to be done before we can answer the most basic, statistical questions about the polarimetric properties of different groups of hot, luminous stars. Insight into the diagnostic power of polarization observations has been gained, but cannot be exploited without detailed models. Thus, while polarimetric observations do tell us that the mass-loss processes of all types of massive stars are time-dependent and anisotropic, the significance that this might have for the accuracy of their stellar parameters and evolutionary paths remains elusive.