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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Outbreaks of light rain or drizzle expected around the coast and hills.
Mike and Cynthia from Ystradgynlais flew out to the German city for a weekend away.
Fine and dry at first but becoming largely cloudy with outbreaks of rain or drizzle.