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The easiest place to charm a White Tiger is in the northern part of Arborstone, accessed from the Tanglewood Copse or Arborstone outposts. One will usually appear close to either outpost.
In Melandru's Hope, a level 15 White Tiger will spawn near Salke Fur Friend for him to charm. You can prevent this by flagging your heroes/henchmen at his spawn point using the mission map (so that they are outside your compass range); as you approach, Salke will attempt to tame the tiger, but your AI teammates will interrupt and otherwise distract him.