Wasps lock Shaw will be on the replacements' bench when England launch their RBS 6 Nations Championship campaign against Italy in Rome.
He was initially omitted from the England 22 behind Ben Kay, Danny Grewcock and second-row cover Borthwick for Sunday's Stadio Flaminio encounter, but the latter is now in hot water with Rugby Football Union disciplinary chiefs.
The Bath second-row forward has been cited by independent commissioner Peter Larter for alleged foul play on Wasps and England captain Lawrence Dallaglio during a league match last Saturday.
Borthwick will face a hearing next Tuesday but, under RBS 6 Nations rules, he cannot play for his country while a disciplinary matter is pending.
It means England head coach Sir Clive Woodward has been forced to make a change he could have done without, especially given an extensive injury list for his team's first Test match since they were crowned world champions.
"It was a surprise to me and a surprise to Steve," said Woodward. "We didn't find out until we got a call at 8pm on Monday.
"But those are the rules, and we've got to go with them and move on.
"The initial choice in selection was between Simon Shaw and Danny Grewcock to partner Ben Kay in the second row, and then the best (other) player to be on the bench.
"Simon lost out on both decisions and clearly he was annoyed about that. Now though, he has got a chance, and that's what sport is all about."
England's individual and collective discipline has never been a serious problem under Woodward on the Test match stage, and he sees no reason for that to change.
"We speak a lot about it," he added. "It is an absolute key part of the game, and I would like to think that England over the course of the last three or four years have been the most disciplined of teams.
"The referees say that they have never had an issue with England. We are no angels, but we want to play right in people's faces, without conceding penalties or doing anything illegal."