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I got rid of poison ivy by cutting the plants at the ground. The vine will die and you can spray the new growth close to the ground. It might take more than one shot to kill it completely since the roots are probably well established. This method worked for me but I didn’t attempt it under azaleas. Use this suggestion at your on risk.
I’m extremely toxic with poison ivy…Poison oak rarely bothered me as a child, but I got into some poison ivy about 15 years ago and before I knew what was going on, both of my arms were really messed up. It’s so intertwined with the azaleas, I think it’s a lost cause. Sprayed some last year but it was killing the azeleas also.
"Whomp 'em, Up, Side the Head"!