@JFH Yes, you can do that. If you have O365 federated with ADFS and you federate an application with Azure AD, the authentication flow would be:
- User accesses the application which is federated to Azure AD.
- Application will redirect to Azure AD authentication endpoint (https://login.microsoftonline.com) for authentication.
- User will be prompted for credentials.
- Based on the UPN suffix (If the domain is federated with ADFS), user will be redirected to ADFS.
- ADFS will authenticate the user and issue a WS-Fed token to Azure AD.
- Azure AD will receive the token and issue a SAML token to the application.
- User will finally get access to application.
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