Opposition People's Party leader Alberto Núñez Feijóo visited the scene, while King Felipe VI travelled to a hospital in Toledo treating survivors of the disaster. The monarch was greeted by hospital staff and other people waiting outside before entering the building.
Meanwhile, rescue teams continued searching the wreckage with sniffer dogs, as cranes lifted damaged carriages and emergency workers combed through debris scattered down a gravel embankment. One more body was recovered overnight, bringing the death toll to 69, according to Castilla-La Mancha regional president Emiliano García-Page, who said 50 people remained in hospital.
The collision occurred on Wednesday morning when a high-speed train operated by state-owned Renfe struck the rear of a stationary Iryo service in central Spain. At least three carriages were thrown down an embankment by the impact.
The government declared three days of national mourning from Thursday, as the country's second deadly high-speed rail disaster this year raised fresh questions about railway safety.
In January, 46 people were killed in another collision involving Renfe and Iryo trains on the same line. The latest crash, just four weeks before a national election, has also disrupted rail travel, with the high-speed route between Madrid and Seville closed and thousands of passengers seeking alternative transport.