Singular Mueller matrices play an important role in polarization algebra and have peculiar properties that stem from the fact that either the medium exhibits maximum diattenuation and/or polarizance or because its associated canonical depolarizer has the property of fully randomizing the circular component (at least) of the states of polarization of light incident on it. The formal reasons for which the Mueller matrix M of a given medium is singular are systematically investigated, analyzed, and interpreted in the framework of the serial decompositions and the characteristic ellipsoids of M. The analysis allows for a general classification and geometric representation of singular Mueller matrices, which are of potential usefulness to experimentalists dealing with such media.