AbstractPolarization observations yield otherwise unobtainable information about the geometrical structure of unresolved objects. In this talk we review the evidences for non-spherically symmetric structures around Luminous Hot Stars from polarimetry and what we can learn with this technique. Polarimetry has added a new dimension to the study of the envelopes of Luminous Blue Variables, Wolf-Rayet stars and B[e] stars, all of which are discussed in some detail.