He added that those voting to leave the UK to end the prospect of Conservative rule from Westminster would be “cutting off your nose to spite your face”.
The Labour MP also suggested that as chancellor he would help Holyrood redistribute wealth through fairer taxes after the next general election.
And he said that former prime minister Gordon Brown was a “massive figure” in the campaign to defeat independence in Scotland and would be key in promoting the Labour case for a No vote.
Speaking to The Scotsman, Mr Balls claimed a Yes vote would be “disastrous” for social justice in Scotland, and said the SNP would pursue tax cuts for the wealthy under independence.
He said: “If Scotland broke away from the UK it would lead to fewer jobs as well as more unfairness.
“There is an old saying that you don’t cut off your nose to spite your face, and Scotland and the long-term consequences for social justice of leaving the UK would be disastrous.”
But SNP MSP John Wilson said Scotland had been harmed by the actions of successive UK governments.
He said: “The people of Scotland know with certainty that remaining within the UK will guarantee austerity measures on a scale never seen before.
”Scotland has been deprived for decades of substantial investment in the manufacturing sector and since the 1980s we have seen the demise of shipbuilding, steel and mining.”