She had only one surviving brother, Prince Heinrich XXIV Reuss of Greiz, who was incapable of governing because of the physical and mental ailments that resulted from a childhood accident.
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Caroline was a daughter of the reigning Heinrich XXII, Prince Reuss of Greiz by his wife Princess Ida, daughter of Adolf I, Prince of Schaumburg-Lippe.
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Her younger sister Princess Hermine Reuss of Greiz would later marry Emperor Wilhelm II as his second wife.
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