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Hello.
As far as I know, as of August 2024, I don't think there was an option to change the default user of EC2 Instance Connect.
I recommend that you send feedback on the UI from the feedback button at the bottom left of the AWS Management Console, as it should probably be possible to resolve the issue with the UI.
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- AWS OFFICIALUpdated 8 months ago

Thanks, I've sent feedback to AWS, and considering creating a support ticket as well.
For now I'll just manually type ec2-user when logging in via instance connect.