In ancient times, the area was subject to large-scale metallurgical activity, with the largest ancient deposit of slag in Bulgaria.
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In 1903, the residents of Rezovo took an active part in the Bulgarian Ilinden-Preobrazhenie Uprising, seeking unification with their compatriots in the Principality of Bulgaria.
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As the Rezovo River constitutes the border between Bulgaria and the European part of Turkey, Rezovo directly overlooks the Turkish bank of the river and the Turkish village of Beğendik, in Demirköy district, Kırklareli Province.