Scottish Labour leader Johann Lamont urged the First Minister to back a Holyrood bill designed to protect tenants who fall into arrears as a result of the so-called bedroom tax.
She also called on him to make more cash available to support those struggling to pay.
Mr Salmond came under pressure during First Minister's Questions, as Labour launched a consultation on its proposed Protection from Eviction Bill.
Meanwhile, efforts to end the bedroom tax across the UK continued as lawyers representing adults and children with disabilities won permission to challenge its legality in the Court of Appeal.
At Holyrood, Ms Lamont attacked the SNP's decision to provide financial help for struggling tenants only in the current financial year.
She told MSPs: "The reason the Scottish Government is cutting off support for the victims of the bedroom tax is that they see injustice as an opportunity not to help people suffering in Scotland but an opportunity to be exploited ahead of the referendum.
"If the First Minister really wanted rid of the bedroom tax he would be urging voters in England to vote Labour to abolish it."
The First Minister refused to back the proposed eviction ban and said the Scottish Government was doing all it could to mitigate the impact of the bedroom tax under Holyrood's existing powers.
He said: "If we want not to have the bedroom tax, if we want not to have people with disability subjected to humiliation, then why can't we in this country have the power to frame our own welfare system so that it meets the ambitions of the Scottish people?"
Under Labour's plans, tenants who could prove in court they were unable to pay their council or housing association rent as a result of the bedroom tax would be granted immunity from eviction.
The plans have been developed by Govan Law Centre and will go out to consultation. Last night they won support from charities.
Graeme Brown, director of Shelter Scotland, said: "We welcome all efforts to end the iniquitous bedroom tax and keep it on the political agenda."
Children in Scotland also said it supported plans to avoid evictions.
But Mary Taylor, chief executive of the Scottish Federation of Housing Associations, said: "Evictions are a sparingly used but necessary ultimate sanction."
UK Labour leader Ed Miliband confirmed last week he would abolish the bedroom tax if his party won the 2015 election.
The SNP has already promised to reverse the cuts if Scotland becomes independent.
In his budget earlier this month, Finance Secretary John Swinney announced a £20 million fund to help those hit by the bedroom tax, which cuts housing benefit by 14% for those deemed to have a surplus room and by 25% for those with two or more extra rooms.
However, campaigners insist £50m per year is required to compensate tenants fully.
Mr Swinney said £20m was the most he could allocate under DWP rules. He refused to make money available next year he did not want to "let Westminster off the hook".
Labour's social justice spokeswoman Jackie Baillie said the Scottish Government had the power to create a £50m "prevention of homelessness fund" which would help all 82,000 people affected by the bedroom tax.
Meanwhile, south of the Border, an appeal judge ruled 10 bedroom test cases should be heard as they raised issues of public importance. Families are appealing against a High Court decision upholding the legality of new housing benefit regulations.
Lawyers claim they are unjustified and unlawfully discriminate against the weak and vulnerable.