User().Email gets the userPrincipalName of the account, so if your Primary Email Address (exchange) is what you've been storing and comparing against then it will not match. I would hazard a guess that those users have a different Email address to their UPN.
User().Email gets UPN
Office365Users.MyProfile().Mail gets Primary Email address
So yes it is case-sensitive (formatting), but also you may need to use UPN as your compared value rather than email or else use the Office365Users connector to get their actual email address to compare to.
Let me know if this helps you,
Ok, yes last bit of advice I can think of is case-sensitivity
Create a label for your reference email (GovEmail)
Create a label for your User().email
Create a label for your Office365Users.MyProfile().Mail
Then create labels to compare each to GovEmail, this should help flag any issues with it not detecting
Additionally, when I compare email addresses, I always try use Lower(EmailAddress) and Lower(comparedvalue)
That way they are both comparing lowercase values.
Give that a try and let me know, we will have to rethink about how we can get around this if those don't show any issues
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