Luke Robertson, 30, had hoped to begin his journey - entitled Due South - two weeks ago but he was delayed by adverse weather.
Mr Robertson, who decided to undertake the challenge after surviving brain surgery, is raising money for charity.
If all goes to plan, he will spend Christmas on the South Pole.
Unassisted and unsupported, he will receive no outside help such as a re-supply by air, and no support from animals or vehicles.
In an interview last month with the BBC, Mr Robertson - who also has a pacemaker fitted - said his final preparations for the South Pole attempt included eating "three hot dogs a day" so he would put on some weight.
It is estimated he will consume 6,500 calories each day, but burn off about 10,000.
The 30-year-old, who is from just outside Stonehaven, will drag 110kg (17 stone) of his equipment across 730 miles of snow and ice for about 35 days, experiencing temperatures of -50C and winds of 100mph.
Every day, he will consume packets of freeze-dried food - ranging from Thai chicken to spaghetti carbonara - which he will cook on a stove.
Mr Robertson has already managed to raise over Â£34,000 for Marie Curie, exceeding an initial target of Â£25,000 which he had hoped to achieve by the end of the journey to the South Pole.
After arriving on Antarctica two weeks ago, Mr Robertson was delayed as adverse weather delayed his final departure to the starting point of Hercules Inlet.
A break in the weather allowed the finance worker to finally make the journey on Saturday.
Readers can follow his progress on social media, and also track his movements on his website.
An Edinburgh finance worker has begun his attempt to become the first Scot to trek to the South Pole solo, unassisted and unsupported.