The Speaker's wife was booted out of the Elstree compound after receiving fewer viewer votes than fellow nominees Bobby Sabel and Kerry Katona.
Upon hearing the news, Bercow nodded knowingly and hugged her fellow housemates.
The crowd had been cheering for Sabel to be evicted after he was shown to have made Darryn Lyons drink sweat in yesterday's show.
Watch the moment Sally Bercow was evicted from Celebrity Big Brother below:
Bercow exited the house to the sound of Emeli Sande's 'Heaven' and a mixed reception from the crowd.
She confided in host Brian Dowling that she was "embarrassed" to be Celebrity Big Brother's first evictee and joked that viewers were "bonkers" for sending her home.
Dowling confirmed after Bercow's exit that celebrity chef Marco Pierre White will be entering the house this weekend and teased that another star will be booted next Wednesday in a "secret" eviction.
Watch housemates react to Sally Bercow's eviction below: