This chapter provides an overview of the 2002 literature pertaining to the mechanism and kinetics of reactions involving neutral free radicals and radical ions in solution. This overview begins by highlighting significant contributions to our understanding of fundamental classes of reactions: atom abstraction, addition, and fragmentation. Afterwards, rearrangement reactions, which are generally unimolecular variants of these fundamental classes, are examined. Next, the chemistry of radical ions is explored in a section dealing with reactions initiated by single electron transfer. This section deals with reactions which do not readily fall under one of the aforementioned classifications (e.g., pericyclic reactions initiated by single electron transfer). Short sections dealing with radical reactions in biological systems, and new methods of radical generation close the chapter. Interesting examples of the use of radical reactions in synthesis are interspersed throughout this report, however, the coverage of this important area is far from exhaustive.