The £58 billion takeover of the Dutch bank is widely regarded to have destabilised RBS and led to its eventual bailout by the taxpayer during the height of the financial crisis.
But a new book by financial journalist Ian Fraser says that Goodwin twice tried to persuade the partner firm in the takeover, Spanish bank Santander, to back out.
The author claims that the Scot, nicknamed The Shred for his abrasive manner and cost-cutting, wanted to pull the plug on the deal after ABN Amro sold its US business, which was considered its most lucrative venture.
However, he was overruled by Santander's Emilio Botin.
Fraser's book - titled Shredded - claims that Botin threatened legal action if Goodwin and RBS walked away. The author also alleges that Alfred Saenz, chief executive of Santander, later boasted that his firm came out best from the deal, saying: "We are the only ones to come out smiling. We have got the better of our consortium partners."
Fred Goodwin became the public face of the bank's collapse and the subject of much of the public's ire over bankers' behaviour.
He stepped down when his part in the bank's downfall became public knowledge and was later stripped of his knighthood.
RBS declined to comment on the claims contained in the book.