Drugs policy minister Angela Constance welcomed the move, involving drivers with Central Taxis, saying it would save lives.
The cab company is the largest taxi operator in Edinburgh, with 36 of their drivers having already agreed to carry out the necessary training to administer the drug, enabling them to carry it in their vehicles.
Police officers, the ambulance service and members of the Scottish Fire and Rescue Service already carry naloxone.
But as taxi drivers can cover large areas in the course of their work, it is thought they may encounter someone who has overdosed before an ambulance has been called.
Julie McCartney, the Scottish Ambulance Service's drug harm reduction lead for the east of Scotland region, said the service was "delighted to be working with Edinburgh Central Taxis and our local partners, to raise public awareness of the importance of being able to identify an overdose, administer naloxone and call 999 for an ambulance".
She stated: "This forms part of a wider catalogue of work by the Scottish Ambulance Service to maximise every opportunity to support those who use drugs to access treatment and support direct from the scene of an emergency."
And Murray Fleming, company secretary, at Central Taxis, said: "This is a great campaign. Our drivers are out and about 24 hours a day and are very much the eyes and the ears of the city.
"We've had a terrific initial response from drivers registering to complete the training, carry naloxone and play their part in the Stop The Deaths initiative.
"We already provide a back-up service for the NHS and ambulance service in Edinburgh and see ourselves as very much the fourth emergency service."
Ms Constance said: "I welcome this joint initiative by Scottish Ambulance Service and Edinburgh taxi drivers which will result in more lives being saved through the use of the emergency treatment naloxone."
She added: "The response to the Stop The Deaths campaign has been very encouraging and in addition to saving lives, we hope it has helped reduce the stigmatisation of people at risk of overdose and those with a problematic drug use more broadly.