The set was filmed in 2007, when Winehouse was on her way from breakout star to superstar. It was originally taped as part of MTV's "45th at Night" series, set at MTV's Time Square studio.
The Dap-Kings, who backed her on the "Back to Black" album, join Amy on stage for the performance. Rapper Mos Def also makes an appearance to collaborate with Winehouse on the song "Love is a Losing Game."
The performance, which showcases a somewhat healthier-looking Winehouse than the public had become accustomed to seeing, is likely to be an emotional one for its audience. Along with "Back to Black," "Me & Mr. Jones" and "You Know I'm No Good," Winehouse performs "Rehab", which was something of an anthem for the singer while alive, and now has increased significance due to widespread speculation that drug and alcohol use contributed to Amy's untimately death.
The tribute special comes a day after Winehouse's North London funeral, which took place on Tuesday. A private funeral service at Edgwarebury Cemetery in North London was expected to be followed by a cremation and a family gathering.
Amy's close friend Kelly Osbourne - who wore her hair in a beehive as a tribute to Amy's signature look - and producer Mark Ronson were among mourners present.
Winehouse's ex-husband, Blake Fielder-Civil, did not attend the funeral. Blake is serving a 32-month sentence for burglary and firearm possession.
Winehouse was found dead in her north London apartment on Saturday afternoon.
Friends said that soulful singer had engaged in "wild drinking" in North London in the days preceding her death.
"There was always a danger of something like this," one friend told The Mirror. "Her drinking is totally out of control. She's constantly out of control on vodka. She'd drink bottle after bottle and mixing those quantities with drugs is lethal."
But Kelly Osbourne - who spent an hour on the phone with Winehouse the day before she died - did not believe her friend to be in any immediate danger.
"I was speaking to her last night, she seemed absolutely fine, I don't understand how this could have happened," Osbourne told the Mirror.
Winehouse had spoken to her security guard, Andrew Morris, on Saturday morning at about 10 am, and told him she wanted to go to sleep. That is believed to be her last conversation.
When Morris went to wake her several hours later he found her dead.
"Rigor mortis had set in," a source told The Sun, "indicating she is likely to have been dead for anything up to six hours."
Police sources told the UK newspaper that there were no signs of drugs at the house.
Witnesses had earlier reported seeing Winehouse buying a variety of drugs in Camden around 10:30 pm on Friday night. A source told The People that the singer bought cocaine, ecstasy, ketamine and possibly heroin.
"Amy seemed determined to have a big one on Friday night," the source said. "She was out in Camden on Friday evening, but seemed determined to carry on the party back at her flat.
"None of us know who was with her into the early hours of Saturday. But getting out of it was clearly her main priority of the night."
Amy's family told The Sun these reports were "nonsense."
Amy had seen a doctor on Friday evening, and she received a clean bill of health.
She had been getting regular checkups because of the overall toll her lifestyle had been taking on her body.
"The doctor was happy with her condition," a source told The Sun. "When he left on Friday night he had no concerns. Less than 24 hours later she was found dead."
An autopsy was conducted on Monday but the cause of death will not be known until the toxicology report is completed - which could take up to four weeks.
Amy saw her mother, Janis Winehouse, the day before she died, and Janis was concerned for her well-being - as she often was.
"She seemed out of it. But her passing so suddenly still hasn't hit me." Still, Janis Winehouse felt that it was "only a matter of time" before tragedy took her young daughter.
Winehouse's father, a jazz musician and part-time taxi driver, was in New York City when he heard of his daughter's death. He had been scheduled to perform at the famous Blue Note jazz club. In what may have been Amy's last public comment, she wrote "I'm very proud of my dad," in an email to the New York Post on Friday.
Her father, who immediately returned to London upon hearing the news, is "devastated" by the loss.
A few days before her death, Mitch Winehouse also spoke to the New York Post about his daughter.
"Frankly she's had her ups and downs," he said.
"Our family has been left bereft by the loss of Amy, a wonderful daughter, sister, niece," Amy's family said in a statement.
The Amy Winehouse tribute special will air on MTV on Wednesday, July 27, at 6:30 pm EST/PST.