The Government has set up a £1.7 million fund to provide support to advice services while a further £3.4 million will be spent over the next two years to help organisations mitigate the impact of welfare reforms.
Meanwhile, Citizens Advice Scotland (CAS) and other advice agencies will be given an immediate £300,000 cash injection.
CAS last week reported an increasing demand for its services and warned that this was likely to get worse as further changes to the welfare system come into force.
Benefits reforms passed by Westminster last year include the introduction of the new Universal Credit and changes to Child Tax Credit, Working Tax Credit and Housing Benefit.
Deputy First Minister Nicola Sturgeon said: "Many people across Scotland are suffering as a direct result of UK Government benefit cuts and many more are concerned about how they may be affected by changes yet to come into force.
"Citizens advice bureaux across the country are currently dealing with nearly 800 new issues for every working day.
"It is clear that the impact of the cuts will extend across Scottish society, with vulnerable groups, women and working families all likely to suffer.
"This is putting more and more pressure on the organisations that provide crucial frontline advice to those affected.
"These are the people, who, on a daily basis see how lives are being damaged by the fall-out from the UK Government's welfare reform changes.
"That is why we have listened and are providing £5.4 million to help meet the demand for advice and support as it dramatically increases."
CAS chief executive Margaret Lynch said the money would be used to train more advisers and provide longer hours of service.
She said: "Bureaux across the country are already dealing with unprecedented levels of need due to current welfare changes and benefit cuts.
"We already can see the damaging aspects of cuts and changes on the lives of families and household across the country, and more is set to come over the next few years.
"We are, therefore, delighted that additional funding is being made available by the Scottish Government for all advice services across Scotland to help cope with the increased demand. It is much-needed and will be well-used."