It depends on whether you mean the coach with the most wins (longevity stat) or the coach with the highest percentage of wins in his career. Paterno is the leader among active coaches in number of wins. Although technically he is no longer active as of end of 2011.
Highest win percentage will depend on how many seasons you set as the minimum for the stat. Obviously a coach could be 100% after 1 season, so it makes sense to set a bar of at least 5 or 10 seasons.
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