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In their analysis of experiments and in their planning of syntheses, organic chemists consciously or unconsciously tend to use the principle of least motion, the chemical equivalent of Occam’s razor. In rearrangement reactions this principle is violated and may make rearrangements problematic reactions. At the same time, there is always fascination in the unexpected and so rearrangement,reactions are also an attractive field of study. The present account is meant to spread this knowledge. In addition, an introductory chapter gives a survey of the basics of organosulfur chemistry to put the information in the individual chapters into perspective and to help readers who are less familiar with the peculiarities of sulfur in an organic environment.The amount of material requiring coverage was so vast that the volume had to be split into two parts.