@B3655, Thanks for posting in Q&A. From your description, I know we have deployed policy "Configure TPM startup PIN: Require startup PIN with TPM" to device, it shows successful, but PIN is not prompted.
Here, please manually run the following command to see if it can work.
manage-bde.exe -protectors -add c: -TPMAndPIN
Meanwhile, we can check the Event log under Applications and Services Logs > Microsoft > Windows > BitLocker-API.to see if any related error existing.
Please try the above suggestion and if there's any update, feel free to let us know.
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