Firefighter Barry Martin has died of his injuries sustained when battling the fire at the former Jenners Department store on Monday this week.
In a statement interim Chief Officer Ross Haggart said: "It is with profound sadness that I confirm, on behalf of his family, that Barry Martin has passed away this afternoon following the serious injuries he sustained during a large-scale fire at the former Jenners building in Edinburgh."
Martin was one of five firefighters taken to Edinburgh Royal Infirmary on Monday. Four of the firefighters were released on the same day from hospital but Martin was being treated for serious injuries and had been in a "critical condition".
"I speak for the entire Service when I say that we are all devastated by the loss of Barry and our thoughts remain with his family, friends and colleagues at this deeply distressing time," said Haggart.
"Both Barry’s family and the Service have been overwhelmed with the messages of support we have received and we thank everyone for the time they have taken to share these."
At its height, over 100 firefighters battled the blaze on the lower floor of the landmark Edinburgh building and were able to prevent the fire spreading from the 1905 Rose Street extension throughout the whole building.
“Barry’s family would also like to thank all the medical staff who have cared for him," Haggart added.
"I would now ask that we all allow Barry’s family, friends and colleagues to grieve in private."