Sounds like it should work, but if it doesn't try the following: 1. Click the segue that doesn't work and give it an identifier. Let's say it's PopoverToNewSegue.
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In your implementation file for the popover view controller, add an action when the button is clicked.
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That function should return void and add the following line: [self performSegueWithIdentifier:@"PopoverToNewSegue" sender:self];
That should get your segue running. I've noticed that segues don't always work like you expect them to, but this one works for me without fail.