Michael Vels is expected to play a key role in Hydro One's plan to sell shares to outside investors through an initial public offering.
His appointment is effective July 1.
The chairman of Hydro One's board of directors, David Denison, says Vels has experience in mergers and acquisitions that will be valuable as the utility firm undergoes the transition to a publicly traded company.
The Ontario government hopes to raise $9 billion from the partial sale of Hydro One, with $5 billion earmarked for hydro debt and $4 billion going to public transit projects.
Prior to joining the Canada Bread bakery arm of Maple Leaf Foods in 1991, Vels worked in the United Kingdom and trained in South Africa as a chartered accountant.
Vels left Maple Leaf (TSX:MFI) last year after it sold Canada Bread to Grupo Bimbo of Mexico, one of the world's biggest bakery companies.