James joins from Direct Line Insurance Group where she has been chief executive officer for the past two years, having joined the company as chief financial officer in November 2017.
She previously held a number of roles at Prudential including group chief risk officer and director of group finance.
Prior to this James was group CFO at Omega Insurance Holdings and CFO of UK general insurance at Zurich Financial Services.
She was also a non-executive director of Admiral Group from 2015 to 2017.
According to Hargreaves Lansdown, James brings extensive financial services experience with “strong leadership skills, financial and risk expertise, strategic thinking and cultural alignment”.
Deanna Oppenheimer, chair of Hargreaves Lansdown, said: "I'm delighted to welcome Penny to the group board. She brings exceptional skills with broad ranging financial services experience - in particular in leading digital innovation and transformation - and supports the continued strengthening and diversity of the group board."
When she takes up her role, she will also join the board risk committee and nomination committee.
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