Police Scotland officers launched raids alongside Merseyside Police's Matrix Serious Organised Crime unit.
William Williamson, 31, of Perth, and Candice Gorman, 31, and Donald Campbell, 46, both of Irvine, will now be interviewed by police in Liverpool.
All three are charged with conspiracy to supply controlled drugs.
The Scottish arrests follow the charging of 22 people in Merseyside, South Wales, Devon and Cornwall last week after a series of co-ordinated dawn raids led by Merseyside Police.
Large quantities of Class A drugs, cannabis and cash were recovered during the searches.
Three people from North Ayrshire and Perth have been charged with drugs offences following their arrests as part of a UK-wide police operation.