Jones took the lead on his 1968 hit with Pavarotti adding his own parts in his native Italian.
The pair sang a rendition of the hit single Delilah at the tenor's annual charity concert in aid of Afghan refugees.
Jones took the lead on his 1968 hit with Pavarotti adding his own parts in his native Italian.
Pavarotti also performed duets with stars such as soul legend Barry White and British female string quartet Bond.
Pavarotti joined Anastacia and Morcheeba for the show, with proceeds from the event going to the United Nations refugee fund.
Zeta Jones
Among the guests at the concert in Pavortti's home town was Swansea-born actress Catherine Zeta Jones and her husband Michael Douglas, who like Pavarotti is a UN peace envoy.
Past concerts have seen Pavarotti sing with Bono, George Michael and the Spice Girls.
He has expressed his wish to sing a duet with Madonna in the future.
A choir of Afghan children joined in the fund raising event.
Jones himself recorded an album of duets called Reload, releasing hit singles with Robbie Williams and Welsh bands Catatonia and the Stereophonics.
The charity bashes have raised millions of pounds for children's charities around the world, aiding medical and educational needs in places such as Liberia and Tibet.
Pavarotti said: "There is an enormous need for basic education and health care amongst the Afghan refugees.
"It is a relentless, cruel situation for these children and worsens each day."
Pavarotti was one of the first opera singers to bring the musical genre to a wider audience.
As one of the Three Tenors, with Jose Carreras and Placido Domingo, he transformed Nessum Dorma into a football anthem, performing it at three World Cups.
He has recently been embroiled in a tax evasion case, eventually agreeing to pay 25 billion lire (£8m) to Italy's finance ministry to settle.