"The NHS under his watch is failing."
Johann Lamont hit out on the issue a week after Health Secretary Alex Neil survived a motion of no confidence in Holyrood and days after official statistics showed the NHS is missing key targets.
During First Minister's Questions, she cited the case of a woman who found a lump on her breast who was "forced to pay for private healthcare" after weeks of worry when she did not receive a hospital appointment for cancer screening.
Mr Salmond said that while some areas do "need to be improved", there has been a "very substantial improvement" in the health service compared to when Labour was last in government.
Ms Lamont told Mr Salmond: "The Scottish Government has missed its 18-week waiting time target from referral to treatment.
"It still, month after month, fails to hit its target of treating A&E patients within four hours, even after diluting the target. Bed blocking - which means people are left languishing in beds because the care system has nowhere for them to go - has gone up 300 per cent.
"The NHS is now going backwards on his watch."
She added: "Can the First Minister remind us, why does he still have confidence in his Health Secretary?"
Mr Salmond said the NHS in Scotland is "still something in which we can be really proud". He added: "The statistics that we're seeing now, although not ideal, and in some cases still to meet the targets to which we aspire, are in every single case superior to those when the Labour Party left office."
He said that in April 2006, then Labour health minister Andy Kerr had hailed figures showing 87.5 per cent of A&E patients were treated in time as "showing the vast majority of accident and emergency departments are meeting the four-hour target" and that "investment and reform in the national health service is paying off".