Maj Gen Alenka Ermenc, 55, will take charge as chief of staff on Wednesday, BBC reported.
A former army commander, Ermenc began her military career in 1991, when the country gained independence from Yugoslavia.
President Borut Pahor said he hoped she would improve the army's performance. Earlier this year, a Slovenian army brigade failed a Nato combat readiness test, the BBC report said.
Ermenc graduated from the Royal College of Defence Studies in London and completed a Master's degree in International Studies at London's King's College University.
Slovenia, the home country of US First Lady Melania Trump, has an army of 7,500 soldiers.
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