railing in fifth following the downhill section, the German powerhouse put the hammer down through the 59 tricky gates on the Rosa Khutor course to snatch her third Olympic gold with a combined time of 2:34.62.
The tall 29-year-old customs officer from Garmisch only needs one more victory at this Games to equal Croatian Janica Kostelic's all-time record and she will start as favourite to win Wednesday's downhill.
Julia Mancuso, who was second to Hoefl-Riesch in Vancouver four years ago, had set the pace in the downhill section of an event that tests the full range of skiing skills, building a one-second advantage over the German.
However, despite a battling effort on her less favoured slalom discipline the American leaked too much time and ended up third, with experienced Austrian Nicole Hosp moving through the field to take silver.
Rising Swiss Lara Gut, second after the downhill, was one of nine skiers who failed to reach the bottom of a testing slalom course that became bumpy in the mild conditions.
As the brass band pumped up the atmosphere at the mountain venue, Hoefl-Riesch bombed out of the starting gate for the slalom and produced a near perfect descent to capture the first women's gold of the Alpine skiing programme at the Sochi Games.
Swerving with rhythmic precision through the red and blue poles she looked in total control as she put down an ominous marker to her main rivals in the Caucasus Mountains.
"It was a big fight and it wasn't easy because the snow was tough and bumpy," she told reporters.
"The hill was steep at the start, which I found especially difficult. It didn't feel great, but I skied fast enough.
"I was able to keep my skis going and didn't brake too much in the turns. Julia was hot in the downhill and I was nervous because she was leading by a second."
Despite failing to hold her halfway lead, former Olympic giant slalom champion Mancuso looked delighted to cling to a podium spot, 0.10 seconds ahead of Slovenian all-rounder Tina Maze, and warmly embraced Hoefl-Riesch in the finish area.
"I feel amazed," Mancuso, who dedicated her medal to her late grandfather, told reporters after claiming a medal from a third consecutive Olympics.
"This has been an unbelievable day. To win another medal is just a dream come true. I dedicated this to my grandpa.
"He had always encouraged me, but he passed away a year ago. We had hoped he would make it to this Games, but it's a great feeling that he has been watching from above."
Hosp was also thrilled to add to her Olympic medal collection, eight years after a slalom silver in Turin.
"Sometimes you get on a roll at the Olympics," she said. "My goal was to win a medal and now I've got one.
"Now I can set off completely relaxed for the next races. Anything more that's to come will be a bonus."
The action comes thick and fast with the downhill on Wednesday when overall World Cup leader Hoefl-Reisch will start as favourite despite her playing down her chances.
"This is my last Olympic Games for sure," she said.
"I knew this would be the best chance for a medal, and I knew it would be difficult to get one if I didn't win today."