The accident happened about 1.5 miles (2.4km) south of Pathhead, Midlothian, at around 7.30am.
A gold-coloured Nissan Note carrying five people was in collision with a silver Skoda Octavia and ended up on its roof, Lothian and Borders Fire and Rescue said.
The female driver of the Nissan managed to get out before emergency services arrived and fire crews cut one man free.
Three male passengers sitting in the back of the Nissan died at the scene, Lothian and Borders Police said.
The man cut free from the overturned car was taken to Edinburgh Royal Infirmary along with the female driver and the male driver of the Skoda. Their injuries are not life-threatening.
The A68 is closed while officers investigate the crash.
Inspector Simon Bradshaw said: ‘This is a tragic incident and we are currently in the process of carrying out inquiries in order to establish the full circumstances of the collision.
‘At this time I am appealing to anyone who noticed the gold-coloured Nissan Note or the silver Skoda Octavia on the A68 this morning to get in touch.
Meanwhile, a man and a woman died yesterday in a head-on crash around 10 miles from today’s fatal collision.
Two other people are being treated in hospital after the accident on the A697 in Carfraemill in the Scottish Borders at around 2.55pm yesterday.
A 53-year-old man and a 51-year-old woman were travelling south in a silver Kia Cee’d when it was in collision with a red Hyundai I30 driving north.
The woman died at the scene and the man died in Edinburgh Royal Infirmary, Lothian and Borders Police said.
Two people in the Hyundai were also taken to hospital.
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