She joins The Co-op from insurance and travel assistance firm CPP Group, where she was HR director.
Duducu said she was "delighted" to be joining The Co-operative Group at such a "significant moment in its history".
"It's been a difficult year for the group, but I am joining a new leadership team that has begun to put in place a long-term strategy for the revival of the business," she said.
"The innovative and pioneering values of The Co-op are going to remain central, and HR will be playing a lead role in reshaping the business. It's great to be part of a very exciting journey."