Poison Ivy wouldn't have me thinking rash
Poison ivy is a plant that causes skin rashes. To think rashly however, means to think quickly and often irrationally. Em could also mean he’s so crazy he couldn’t think rash (short for rationally)
And, of course walking on the path, you might get actual poison ivy.
This line also calls back to the Batman reference in the first verse: Poison Ivy is one of Batman’s enemies who uses sexuality to seduce men; however, such seductresses have no power over Eminem
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