The Edinburgh Bar Association (EBA) has confirmed all of its criminal law members – 31 firms – will not take part in the Police Station Duty Scheme for Edinburgh Sheriff Court in the first quarter of 2013.
Police station detainees – who can only be held for a maximum of 24 hours – must be offered access to a lawyer and the scheme ensures that solicitors are available day or night.
But the move by the EBA could cause serious delays for police waiting to interview suspects.
Other associations are expected to join the EBA in protest at controversial plans by the Scottish Government to change legal aid.
A spokesman for the Scottish Government said: "This action by the EBA, which seeks to put the criminal justice system at risk for the convenience of solicitors, is extremely disappointing and attacking the police station duty scheme in this way is totally unjustified."
The Scottish Legal Aid Board (Slab), which runs the scheme, added that action "appears to risk damage to the justice system".
Cameron Tait, EBA president, said the action may cause delays in policing. In a letter to Slab, he said: "This is in protest at the planned expansion of contributions in criminal legal assistance and their collection.
"It is also a protest against the position adopted by Slab and the Justice Secretary in the public domain over these issues.
"This Association is of the view that Slab and the Scottish Government are making little secret of the lack of value they attach to the service which is provided to the public and to the Criminal Justice System as a whole by the independent criminal bar in Scotland."
Justice Secretary Kenny MacAskill wants those with a disposable income of £82 a week or more to pay a contribution to their legal aid, but lawyers claim this will limit access to justice.
The Government also plans to force lawyers to collect the contributions from their clients.
Mr Tait added: "Slab and Government ministers refuse to discuss sensible alternatives for collection of summary contributions. We believe it is clear that Slab is now directing Government policy, is capable of riding roughshod over the considered views of Parliamentary Committees, and is pursuing a policy of attrition against the independent criminal bar."
The lawyer confirmed that three other associations are planning to take similar action.
The Government spokesman added: "Contingency arrangements will be put in place to minimise the impact of any action and the Justice Secretary will instruct Slab to take any and all action that is necessary to ensure the right of those being questioned in police stations to access legal advice is upheld.
"Officials will also discuss this issue with the Law Society when they meet representatives on Wednesday next week."
A spokesman for Slab said the EBA's claims were "ludicrous", saying that the board's statutory role includes advising Ministers on legal aid.
He added: "We will provide police station duty scheme cover for the Edinburgh Sheriff Court area from January. We are aware that firms will undertake this work and we will make other solicitors available."