Libbok's highlight was a second-half no-look assist for Kurt-Lee Arendse as the Springboks began their search for a record fourth Webb Ellis trophy in clinical fashion in the Marseille heat, winning 18-3.
Former World Player of the Year Pieter-Steph Du Toit had crashed over earlier in the tie for Jacques Nienaber's outfit in Pool B.
Their next major test to reach the quarerfinals will be world No 1 side Ireland on 23 September, six days after facing Romania.
"I think it could have been a slippery one. Scotland are a good side, they are not No 5 in the world for nothing," Nienaber told the BBC.
"I thought we had a little bit of dominance in the first-half but we had to grind the win out."
Earlier in the game, Springboks centre Jesse Kriel avoided a yellow card despite making contact with the head of Scotland No 8 Jack Dempsey during a tackle.
It was a similar incident which led to Tom Curry being shown a red card in England's victory over Argentina on Saturday, raising questions about consistency in refereeing decisions just three days into the tournament.
"It looked like a head-on-head collision and I was expecting the TMO (television match official) to come in," said Scotland head coach Gregor Townsend.
FIJI LATE COMEBACK
Wales began their campaign by overcoming Fiji 32-26 in Bordeaux, avoiding defeat to the highest ranked side in Pool C.
Winger Josh Adams claimed one of four tries for Wales as experienced flyhalf Dan Biggar crossed the 100-point mark for his country at World Cups, surpassing Neil Jenkins' 98-point record.
"You can never write Fiji off. Right at the end they could have won the game," Adams told S4C after his side led by 18 points with less than a quarter of an hour to play.
"We don't want another game like that," he added before next Saturday's match with Portugal.
Fiji, coached by ex-Newport lock Simon Raiwalui, had launched a late comeback thanks to tries from Josua Tuisova and Mesake Doge in the final seven minutes but they were unable to repeat their famous 2007 World Cup victory over Wales.
The Pacific islanders had a lot of confidence before the game, especially after last month's first ever win over England, and they would have felt frustrated by referee Matthew Carley's reluctance to show yellow cards to ill-disciplined Wales.
Fiji will now have to target next Sunday's game with Australia if they are to keep alive their hopes of a first quarterfinal spot in 16 years.
EARLY CHILE SURPRISE
Earlier in the day, 2019 World Cup hosts Japan beat debutants Chile 42-12 despite conceding a try after just six minutes in Toulouse in Pool D.
Brave Blossoms lock Amato Fakatava crossed twice but there was also a controversial tackling incident, reminiscent of Curry's dismissal.
Just before the break, Los Condores captain Martin Sigren was shown a yellow card for a high-challenge on Japan's Kotaro Matsushima, where the two players' heads made contact.
An extra positive for Japan is captain Kazuki Himeno is set to return from a calf injury in time for next Sunday's encounter with 2003 champions England.
After a three-day break, Thursday sees hosts France play their second game of the competition when they face Uruguay, who stunned Fiji in 2019, in Lille.
Les Bleus clinched an impressive tournament-opening success over New Zealand on Friday.
