The former owner had an untaxed £6.3million paid into an Employee Benefit Trust (EBT) set up by the club, according to a BBC documentary.
He was one of 72 Ibrox staff – including 55 players and five former managers – who benefited from the scheme, the programme said.
Rangers use of EBTs to pay their staff has led to an ongoing dispute with Her Majesty's Revenue and Customs (HMRC), who are pursuing the club for millions in unpaid tax bills.
But the documentary gave a list of all the Rangers staff who used offshore financial vehicles for the first time.
The second-highest figure allegedly paid out to an official was £1.7m to Alex McLeish, who managed the club between 2001 and 2006 and was last week sacked by Aston Villa. It was claimed his predecessor in the dugout, Dick Advocaat, received £1.5m
Frenchman Paul Le Guen, who lasted less than a season, is alleged to have received £201,250. Another former manager, Graeme Souness, was said to have been given £30,000.
Former director, manager and player John Greig received £40,000 from the club's EBTs, commercial director Robert Reilly £105,000, and former secretary Campbell Ogilvie, now the Scottish Football Association's president, was given £95,000 over five years.
Sir David denied he saw any benefits from club's use of EBTs, telling the programme: "I personally have never received any payment for any trust which involves contributions coming from Rangers Football Club."
The BBC said the others declined to comment on their alleged EBT schemes.
HMRC has launched a legal action against the Old Firm club claiming its EBTs were used to avoid paying income tax and have gone to court to claw back £35m in unpaid tax and interest, plus £14m in penalties.
The BBC documentary, The Men Who Sold The Jerseys, said a total of 111 trusts were set up between 2001 and 2010 for Rangers directors, players and other staff – along with employees of Murray International Holdings and its subsidiary companies.
But, aside from Sir David, it is the playing and managing staff who won Rangers so many trophies who were apparently the biggest winners from the scheme.
The BBC, which said it had accessed documents proving the payments, claimed ex-captain Barry Ferguson was the highest earner – receiving a total of £2.5m that no tax was paid on.
German goalkeeper Stefan Klos, signed in 1999 for £800,000, was given £2m, while the club's record signing, Tore Andre Flo, from Chelsea for £12m, was paid £1.3m. The Norwegian striker was sold on at a loss to Sunderland in 2002.
Dutch midfielder Ronald de Boer, who spearheaded Dick Advocaat's team, was also paid £1.2m, while Scotland winger Neil McCann's renumeration amounted to £500,000.
Other big names paid through the EBT scheme were ex-captain Lorenzo Amoruso (£639,000), Dutch right-back Fernando Ricksen (£684,225) and Scottish defender Alan Hutton (£364,000).
But it was not just the first-team who were paid through EBTs. Their use appears to have become so deeply ingrained at the club that even players who barely kicked a ball saw their wages arrive without having passed through the hands of the taxman.
The BBC said the documents show Argentinian striker Federico Nieto, who played just three matches in 2005, was paid £24,500 through an EBT, while Italian left-back Paolo Vanoli, who scored just one goal in 28 games in 2003, was given £592,000.
Meanwhile, Stephane Wiertelak, the physiotherapist during Paul Le Guen's brief tenure, was given £28,275. It was alleged the average amount paid to Rangers and Sir David 's Murray Group employees was about £445,000.
Paul Clark, of Rangers administrator Duff & Phelps, said: "The use of EBTs at Rangers goes back many years and was a matter of public record in the annual accounts. Our primary focus has been ensuring the survival of Rangers Football Club and attracting a new buyer for the business as well as investigating the financial situation at the club since the takeover in May 2011.
"We and the club will continue to give every assistance to the football authorities on issues affecting the club. It should, however, be noted that the First Tier Tax tribunal has yet to publish its findings in relation to the use of EBTs."
l An internet blog on the details of the Rangers tax case last night won a prestigious literary prize.
The website, Rangers Tax-Case, was named as the Blog Prize winner of the Orwell Prize at a ceremony in London.
The judges praised it for providing "the details of what Rangers FC have done - what the implications are for one of the largest football clubs in Britain".