Catalonia will declare independence "in a matter of days", the region's secessionist leader Carles Puigdemont was quoted as telling the BBC, a move that would defy Madrid and attempt to implement the directive of Sunday's banned independence referendum.
"We'll probably do this when we have the votes in from overseas, at the end of this week or thereabouts, so we'll act at the end of this week or the beginning of next week", Carles Puigdemont told the BBC in his first interview since Sunday's referendum.
King Felipe didn't mention the nearly 900 people who reportedly required medical care after Spanish police and security forces tried to prevent Catalans from voting Sunday, causing violent clashes.
In a TV address, Mr Puigdemont accused the king of adopting the Spanish government's position.
Puigdemont said there was now no contact between the government in Madrid and his devolved administration.
The European Parliament is holding a special plenary session debate dedicated to the events in Catalonia.
The king's televised speech is extremely unusual.
On Tuesday, the Spanish monarch said, "They have broken the democratic principles of every rule of law and have undermined harmony and coexistence in Catalan society itself, unfortunately coming to divide it".
Barcelona's announcement came barely 20 minutes before the scheduled 3.15pm BST kick-off time and followed hours of uncertainty over whether the game would go ahead.
On Sunday, Catalonia held the referendum on independence, which is considered illegal by the Spanish central government.