He resigned from the BBC One show in 2000 to join an internet auction company launching an antiques business.
Former Nationwide presenter Sue Lawley remembered Scully as a "great talent" who was "fun-loving" and most proud of his interviews with Margaret Thatcher.
Peter Salmon, who was controller of BBC One between 1997 and 2000, said Scully`s "incredible" 19 years at Antiques Roadshow had won him "a special place in the hearts of so many".
He added: "Hugh was a great servant of the BBC for more than 30 years. He was a wonderful journalist and presenter.... he will be sadly missed."
Scully left Antiques Roadshow because it was feared his new role would jeopardise the programme`s reputation for not favouring the expertise of any one auction house.
At the time of his departure, he described the programme as always "a delight and one of the best jobs in broadcasting".
Scully interviewed Baroness Thatcher in 1993, following the publication of her memoirs.
Recalling his first meeting with the former prime minister ahead of the interviews, he told The Independent, he feared things had gone awry.
"She really wasn`t interested in the programmes. I would have expected a lot of questions about what was involved. I went away thinking the meeting hadn`t gone well."
Scully`s son Oliver said his father had died on Thursday afternoon while watching television at his Cornwall home.
Sue Lawley, who worked with Scully on Nationwide and before that at the BBC in Plymouth, added: "He was a very good presenter - he did the most marvellous pieces for camera and he could write, which was terrific.
"His greatest coup, in his view, was when he persuaded Mrs Thatcher to give him the series of programmes they went on to do together on the Downing Street years.
"In the end he and Mrs Thatcher became firm friends."
Henry Sandon, who worked with Scully on Antiques Roadshow, said he had had an "immense ability to drink wine" and was "always happy, jolly and wonderful".
He added: "I shall never forget the chap, he was ever so marvellous."
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