Details of the deal were not immediately available.
The union represents nearly 3,000 workers at Bell Aliant in the Atlantic provinces.
Unifor says ratification meetings will begin next week and results of the vote will be known by Oct. 30.
If ratified, the new contract will take effect on Jan. 1, 2015, a day after the current three-year deal expires.
BCE Inc. (TSX:BCE) announced an agreement earlier this year to take Bell Aliant private and fold its operations into its own. The deal is expected to close Oct. 31.