With the Coalition's welfare reforms emerging as a key political issue of 2013, the Deputy First Minister signalled they would also be pivotal to the independence campaign, with the SNP arguing "leaving welfare to Westminster" is too risky.
She said a raft of planned benefit reforms was already set to cut more than £2.5 billion from Scottish household incomes, while a proposed 1% cap on annual benefit rises for the next three years would cut another £210 million in real terms.
MPs are due to vote on the 1% cap on Tuesday in Westminster.
Labour are refusing to support the bill, which the Tories say helps "strivers not skivers".
Shadow Scottish secretary Margaret Curran last night claimed more than 260,000 working families in Scotland would suffer from the changes to tax credits, with the average family losing £279 per year.
Sturgeon's announcement develops her recent argument that independence would make Scotland a fairer society, an argument pitched at the Labour and LibDem swing voters needed to secure a Yes vote in 2014.
Sturgeon said: "The only way to guarantee social justice in Scotland is to have control of the powers needed to deliver it.
"With a Yes vote in 2014 we would begin work to establish a welfare system that better reflects Scotland's values and ensures fair and decent support for those that need it most – a system that protects the vulnerable and supports households rather than seeing them be subjected to unfair ideological benefit cuts from Westminster.
"The announcement of the expert group is the first step in the journey towards creating a welfare system which will support the economy and society of an independent Scotland."
However, Sturgeon did not identify any specific policy initiatives in the event of Scottish independence.
The members of the new expert group are: Darra Singh, a former chief executive of Jobcentre Plus now working for Ernst & Young; Martyn Evans, chief executive of the Carnegie Trust and former head of Citizens Advice Scotland; Douglas Griffin, a former finance director at NHS Greater Glasgow & Clyde; and Mike Brewer, a professor of economics at the University of Essex and a research fellow with the respected Institute of Fiscal Studies.
The four, who are expected to make an initial report to ministers by May, will advise on a "fairer welfare system" outside the union.
Specifically, they will "provide assurance" on the Scottish Government's cost estimates for the benefit system at the point of independence, and on its plans for delivering welfare payments.
The group will also offer views on which of the Coalition's changes to working-age benefits should be an "immediate priority for change" in an independent Scotland, to ensure the system protects the most vulnerable and helps those who can work to get sustained employment.
AROUND 200,000 high-earning parents across the UK have already opted out of receiving child benefit ahead of changes coming into force tomorrow.
Unless those no longer entitled to the benefit actively opt out by the end of today, they will continue to receive the money but will then have to repay it through income tax.
Child benefit is currently paid at the rate of £20.30 per week for the first child, and £13.40 per week for each subsequent child. It is paid up to the age of 16, or 18 in respect of children still in full-time education.
As part of the Coalition's cost-cutting reforms, child benefit will cease to be a universal benefit from tomorrow. Instead of all families being entitled, those where a parent earns £50,000 or more will see the benefit cut, with 1% lost for every £100 over £50,000, meaning nothing for those on £60,000.
The change is expected to affect around 1.2 million people.
Treasury Minister David Gauke said there had been 1.2 million visits to the HM Revenue & Customs website explaining the change.
He said: "Something like 200,000 people have opted out, which is slightly above what we'd expect at this stage, so there does seem to be quite a lot of awareness about it."
January: Sliding cuts to child benefit if one parent earns £50,000 or more. Child benefit ends if one parent earns more than £60,000.
April: Council Tax Benefit replaced by new system involving 10% cut in funding to councils. SNP Government is shielding Scottish councils from this cut.
April: Housing benefit cut to reflect house size and "over-occupation": 14% cut for a house with a spare bedroom, 25% cut for two or more extra bedrooms. Around 80,000 claimants in Scotland expected to lose average of £12 a week. Claimant options include pay the difference, move home, or take in a lodger.
April: Phased replacement of Disability Living Allowance (DLA) with Personal Independent Payments, involving cut of around 20% – £260 million in Scotland. Estimated 55,000 people in Scotland expected to lose DLA.
April: Overall benefits cap of £500 per week for couples and £350 per week for single people.
October: Phased introduction of the Universal Credit, gradually replacing housing benefit, tax credits and out-of-work benefits. Paid directly to claimants, not landlords, each month, leading to fears of increased homelessness through rent arrears and bad debts.
Source: Audit Scotland Welfare Reform Update November 2012