Statistics released to the Scottish Liberal Democrats under freedom of information legislation showed 3,652 people waited more than 480 minutes for an ambulance – five of whom were considered the second most severe level recorded by the Scottish Ambulance Service.
The figure amounts to less than 0.7 per cent of total ambulance callouts last year.
At least one person waited longer than six hours for an ambulance after being assessed as a purple call – although the exact number waiting this long is not known because it is lower than five.
Scottish Lib Dem leader Alex Cole-Hamilton said the figures should “set emergency lights flashing” in the Scottish Government.
“When someone is in a moment of crisis and chooses to call 999, they want to know that there will be someone at the other end of the line able to help them,” he said.
“These figures should set emergency lights flashing in the Health Secretary’s office.
“The SNP continuously ignored the warnings of ambulance staff for years. We are now seeing the results of that neglect.
“Scottish Liberal Democrats have called for an inquiry into avoidable emergency care deaths.
“The Health Secretary should admit that he had previously underestimated the scale of the challenge and that the present NHS recovery plan is not up to scratch.
“Swift action might be the difference between life and death.”
A spokesman for the Scottish Government said ambulance crews continue to respond to 99 per cent of high priority calls in under 30 minutes.
It comes as Health Secretary Humza Yousaf is set to make a statement on the NHS statement as sector braces for ‘challenging’ winter.
Mr Yousaf will address MSPs on Tuesday, detailing measures the Scottish Government will take to support the health care system over the winter, as well as updating on progress of the NHS recovery plan announced last year.
His statement at Holyrood will come in the hours after official figures on A&E waiting times and delayed discharges are released – areas where the health service has struggled in recent months.
Before the statement, Mr Yousaf said: “As we enter the winter period it is vital that we maximise and enhance the capacity of the NHS.
“Given the scale of the escalating cost-of-living crisis, combined with the continued uncertainty posed by Covid and a possible resurgence of flu, the winter ahead will be extremely challenging for services.
"I will outline measures we are taking to support winter resilience across our health and care system, ensuring people get the right care they need at the right time and in the most appropriate setting.
“Our NHS and social care staff are key to ensuring we deliver high-quality care for the public throughout winter and I would like to thank them for their continued efforts in the face of sustained pressure on our services.”