@Mountain Pond,Thanks for posting in Q&A.
From your description, I know you want to know the difference in Windows Hello settings in Device Enrollment and through Configuration Policy.
Based on my research, here are some differences between Windows Hello settings in Device Enrollment and through Configuration Policy.
1.Windows Hello for Business settings in Device enrollment is only available during device enroll in Intune and also support Windows Autopilot out-of-box-experience, but Windows Hello for Business through configuration policy is available after device enrollment.
2.Windows Hello for Business settings in Device enrollment is available for All users which means it will apply to your entire organization, but Windows Hello for Business through configuration policy available for both devices group and users' group. When you assign it to device group, all users get prompt to configure WHfB at first-time log on to the device, if you assign it to user group, the targeted user didn’t get WHfB prompt at first log on, until the WHfB policy is synced.
https://learn.microsoft.com/en-us/mem/intune/protect/identity-protection-configure
https://msendpointmgr.com/2022/09/04/manage-windows-hello-for-business-whfb-with-intune/
Non-official, just for reference.
Hope above information can help you.
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