Mid and West Wales Fire and Rescue Service says 11 of its crews are continuing to fight the fire at the National Library of Wales.
It is advising people "to stay away for safety."
This video - from viewer Edward Mulgrew - shows firefighters pumping water onto the library roof earlier.
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It will stay largely cloudy tonight and there will be some further rain around, with central parts perhaps staying driest.
ITV Wales understands the reason for the inquiry call stems from concerns raised at the end of 2016 over a former healthcare support worker.
Plaid Cymru says the Welsh Government must 'show stronger leadership' over fire safety at Welsh tower blocks.