The 49-year-old king abandoned his previously measured tone over tensions with Catalonia yesterday as the standoff dragged the country into its deepest political crisis in decades.
He spoke after hundreds of thousands of Catalans rallied in fury at violence by police against voters during a banned referendum on independence for their region on Sunday.
Catalan regional leaders held the vote in defiance of the national government which brands it illegal - as did Felipe yesterday.
"They have placed themselves totally outside the law and democracy," he said.
"It is the responsibility of the legitimate state powers to ensure constitutional order."
Felipe repeated his earlier calls for harmony between Spaniards, but it was a delicate balancing act for the Spanish sovereign after Sunday's violence.
People watching in a bar in Barcelona whistled and booed after the king's speech.
"It is a real disgrace... Far from solving anything it has added fuel to the fire," said Domingo Gutierrez, a 61- year-old trucker, originally from the southern Andalucia region.
Police unions and political experts warned that Spain's government risks losing control of the north eastern region.
It is considered Spain's worst political crisis since an attempted military coup in 1981, which was defused by Felipe's father, King Juan Carlos I.
Crowds in Barcelona on Tuesday yelled for national security forces to get out of the region, branding them "occupation forces" and raising their middle fingers at a police helicopter circling overhead.
City police put the number of demonstrators at 700,000.
Barcelona football club refused to train as part of an accompanying strike, which also slowed down public transport and paralysed freight shipments in the port of Barcelona.
Pictures of police beating unarmed Catalan voters with batons and dragging some by the hair during Sunday's ballots drew international criticism.
Catalan regional leader Carles Puigdemont said nearly 900 people had received medical attention on Sunday, though local authorities confirmed a total of 92 injured. Four were hospitalised, two in serious condition.
The national government said more than 400 police officers were hurt.
"They are fleeing from hotel to hotel, hiding like rats," said the spokesman for Spain's main police union SUP, Ramon Cosio.
Two hotels said local authorities had ordered them to ask police officers staying there to leave. The officers left and were rehoused in barracks, police unions said.
Spanish authorities "are losing control, it is clear," Javier Perez Royo, a constitutional law professor at the University of Seville, told AFP.
"And the government of the nation is taking steps in a very dangerous direction.
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