Laurel Broten will deliver her report this fall.
Finance Minister Diana Whalen says the review will make recommendations on changes to the tax system and regulations to deal with the province's demographic, fiscal and economic challenges.
She says although Broten is leading the review, it will include input from senior civil servants in Nova Scotia.
Whalen says the province's tax system has never had a comprehensive evaluation and this one will look at the impact taxes, fees and regulations have on economic growth and the business climate.
Broten is a lawyer who resigned from politics in June after serving in a number of portfolios in Ontario's Liberal government including intergovernmental affairs, education, environment, and children and youth services.
In announcing her resignation, she said she was moving to Halifax with her family.
Broten was at the centre of a bitter battle a year ago with Ontario's teachers over wage-freeze legislation.
Nova Scotia has an aging population that has been at the centre of public policy debates over economic growth and immigration.
A recent report said the province is doomed to endure an extended period of economic decline unless population and economic trends are reversed.
The report, written by a five-member panel led by Acadia University president Ray Ivany, said Nova Scotia's population is expected to decline over the next 20 years as young people continue to leave the province to search for work.
By 2036, the province expects to have 100,000 fewer working-age people than it did in 2010, the report said.