Hello @Jude Cosh-Wood,
Thank you for posting your query on Microsoft Q&A.
From your description, it seems that your organization’s users are experiencing multiple MFA prompts when accessing Microsoft Teams and SharePoint for intranet sites upon startup.
Given the policy details you shared, I see that you have set the sign-in frequency to 12 hours in your conditional access policy. Multiple MFA prompts can occur when the "Sign-in Frequency" and "Remember MFA on trusted devices" settings are enabled in your tenant. For more information, please refer to the document on Configuring authentication session controls
Since multiple MFA prompts are not expected behavior, please check whether the "Remember MFA on trusted devices" setting is enabled. You can verify this by navigating to Microsoft Entra ID >> Users >> Per-User MFA >> Service Settings, or by logging into this page: https://account.activedirectory.windowsazure.com/UserManagement/MfaSettings.aspx
If "Remember MFA on trusted devices" is enabled, try disabling it and observe if the issue persists.
I hope this information is helpful. Please feel free to reach out if you have any further questions.
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Thanks,
Raja Pothuraju.