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Is the European Union the greatest political peace accomplishment in modern History?
As for today, we don't know other political structures that permits peace between states, as good as the EU does with such cultural diversity and violent history between those states.
That there has been no war between the Soviet Union and the US illustrates another structure for peace:
Mutual Assured Destruction
There was peace between different countries before the existence of the EU.
Personal bonds between leaders made peace likely in times of monarchy.