In a Games hampered by big-name withdrawals and weakened fields, the arrival of the powerful Grenadian was a welcome sight at a wet and windy Hampden Park.
James took charge of the final from the start and looked in complete control as he finished in a Games record time of 44.24 seconds ahead of South Africa's Wayde van Niekerk and Trinidad and Tobago's Lalonde Gordon.
"I expected to have a great performance," James said. "I can't predict the outcome of the event but all I can do is come out here and try my best.
Blake suffers shock defeat as Simbine takes gold in 100m
"Every championship, every accolade, is unique in its own way and these Games are no different. I think the crowd really makes it special; the stadium was full at 10am, that says something about Scotland and how much they appreciate track and field."
The 21-year-old James has won Olympic and world championship gold, but he said talk of breaking American Michael Johnson's world record time of 43.18 was premature.
"I'm going to be 22 in September," James said. "Michael Johnson set the record when he was nearly 32 so I've got 10 years to work with."
Greg Rutherford, England's Olympic long jump champion, provided further delight for the Hampden Park crowd when the self-proclaimed "Ginger Wizard" posed for selfies after leaping 8.20 to win his first Commonwealth gold.
"It's never an easy road and after what happened last year with injury I wasn't sure if I could carry on jumping. Now I've managed to come away with another title," Rutherford told the BBC.
"I think a few people had written me off thinking I was a one-hit wonder. But I'm here again and will be here again many more times. I want to keep going out there jumping far and winning medals."
New Zealand's double Olympic shot put champion Valerie Adams claimed her third Commonwealth gold medal with a throw of 19.88 and Australia's Kim Mickle won the women's javelin title thanks to a Games record throw of 65.96.
With England's Olympic champion Jessica Ennis-Hill recently giving birth and Katarina Johnson-Thompson pulling out of the Games with a foot injury, Canada's Brianne Theisen-Eaton had little trouble in claiming the women's heptathlon title.
Theisen-Eaton, wife of Olympic decathlon champion Ashton Eaton, finished with 6,597 points ahead of compatriot Jessica Zelinka, while Derek Drouin ensured Canada won double gold after clearing 2.31 to win the men's high jump.
Kenya dominated the women's 3,000 steeplechase and claimed a clean sweep of medals as Purity Cherotich Kirui finished in a time of 9:30.96 ahead of Milcah Chemos Cheywa and Joan Kipkemoi.
One of the biggest cheers of the session was reserved for David Rudisha, Kenya's world 800 metres record holder and Olympic champion, who eased through his semi-final to confirm his place in Thursday's final.
Gemili pulls out of Commonwealth Games 100m final with injury
Scott upsets Chalmers to win 100m freestyle title