Police Scotland, which replaces the eight existing forces, becomes operational in April.
Stephen House has already been appointed chief constable, with the six "critical" assistant chief constables now announced by the Scottish Police Authority (SPA).
The new assistant chief constables will be paid between £90,726 and £105,849 a year, depending on their experience, and will take up their new roles shortly.
They will be based at Police Scotland's interim headquarters at Tulliallan Castle, although the three assistant chief constables with responsibility for local policing are expected to spend a large amount of their time in the community.
SPA chair Vic Emery said: "Our focus as an authority is to ensure that the new police service is ready operationally, legally and financially for day one. Appointing a command team to provide the chief constable with the support he needs has been a top priority.
"The new team is taking shape and the appointment of the assistant chief constables marks another big step forward. Each of them will play a major role in working with us to ensure the people of Scotland continue to get the best possible police service within the resources available."
Mr House said: "The six assistant chief constables who have been appointed will play critical roles in the future of policing in Scotland.
"The team will now drive forward local policing, deliver operationally on organised crime, major incidents, counter-terrorism, public protection and operational support. They will work closely with the deputy chief constables to shape the best possible service for communities to keep people safe."
Scotland currently has eight chief constables, nine deputy chief constables and 13 assistant chief constables, costing approximately £4.8 million a year.
The new force will have one chief constable and four deputies, as well as the six assistant chief constables, costing less than £2 million a year.
Overall, the new force could save £1.4 billion over 15 years by reducing duplication and working more efficiently and effectively.
Mike McCormick, previously deputy chief constable in Dumfries and Galloway, will be the new assistant chief constable for local policing east; Derek Penman, acting chief constable of Central Scotland Police, becomes assistant chief constable for local policing north; and Strathclyde Police Chief Superintendent Wayne Mawson will be assistant chief constable for local policing west.
Lothian and Borders Police Chief Superintendent Malcolm Graham, the current divisional commander for Edinburgh, will take on the role of assistant chief constable for serious crime and public protection; Strathclyde Police Deputy Chief Constable Ruaraidh Nicolson becomes assistant chief constable for crime, serious organised crime and counter-terrorism; and Strathclyde Police Assistant Chief Constable Bernie Higgins will be assistant chief constable for operational support.