The UK government announced a £53m support package earlier this week.
Prime Minister Sir Keir Starmer said the aid would be targeted to help low-income households in rural communities.
About 1.5 million UK households use heating oil. The issue of rising prices is particularly acute in Northern Ireland, where about 500,000 homes use it, almost two-thirds of all households.
Scotland’s energy secretary Gillian Martin said oil prices had been “spiralling” since the war in the Middle East.
She said the UK government’s support was welcome but offered “limited” help to Scottish households.
“That is why the Scottish government is announcing today we will more than double the amount available to support Scottish households struggling with heating oil prices,” said Martin.
“We will commit an additional £5.4m on top of the £4.6m allocated by the UK government.”
