Sima Kamil, currently a deputy CEO at the country's third-largest lender United Bank Limited (UBL), will take charge on June 1, its directors said in a statement.
"She is of course the first chief of any commercial bank and it is a huge step forward in the banking and corporate sectors of Pakistan," Pakistan Stock Exchange Chairman Muneer Kamal told AFP. He described Kamil as a "solid professional".
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Women in Pakistan have fought for decades to secure rights for themselves. Few women have headed any high-profile firms in the country.
Kamal cited Shazia Syed as another female pioneer after she was last year made head in Pakistan of Unilever, a Dutch-British multinational.
"Things are transforming in Pakistan now, the world must know that," he said.
UBL, headquartered in the financial hub Karachi, employs 15,000 people and has branches in 15 other countries, including the US, Qatar and the United Arab Emirates.
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