José Manuel Calleja, 62, was one of the five patients whose condition was described as serious.
His wife is still in intensive care along with three other people at a hospital in the northern Spanish city of Santander.
Seventeen British schoolchildren were taken to the same hospital yesterday morning following the breakfast-time incident at the four-star Hotel Campoamor in the village of Isla near Santander.They were released in the afternoon after being subjected to tests and several hours of observation.
Two of the monitors with them received hyperbaric oxygen treatment.
Another 40 children, believed to be from the same school in Cardiff, were tested and monitored at their hotel as a precaution despite showing no signs of gas poisoning.
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The Spaniards in the hotel were part of a group of OAPs from Malaga who were on an organised trip.
They were staying on the second floor where the leak – though to have been caused by a mis-functioning gas boiler, occurred.
Twenty-one of the 92 people treated in total in two hospitals – the one in Santander and another in the nearby city of Laredo – received hyperbaric oxygen treatment.
The name of the school the British youngsters go to has not been revealed.
They took a ferry back to Plymouth from Santander late yesterday.