Worley finished more than one second ahead of Maze, who has dominated this year's skiing season and has already won gold in the super-G and silver in the super combined in Schladming.
Austria's Anna Fenninger was third, partly making up for the disappointment of crashing when she defended her super combined title earlier in the championships.
Slovenian Maze, the overall World Cup leader this season, paid for a disappointing first run which left her more than one second behind Worley and in fourth place.
Worley, who has an Australian father, thrived on the steep, icy course as she added to the gold won by Marion Rolland for France in the women's downhill.
"It was a really hard and tough course," she said. "I felt very confident because I know I ski really well on difficult slopes, so I wanted to push hard and not make any mistakes.
"The French team has been doing so well and that gave me great momentum, and this huge crowd created a great atmosphere."
Maze admitted she struggled on the first run.
"I had no feeling, it was a bit of a nightmare," she said. "I couldn't find my line and my body was tired, too. I felt a lot of pain in my muscles.
"It has been an intense time here and in the World Cup season and the snow is hard here as well.
"I was lucky to find some positive energy between runs and in the second run, I found the determination I needed.
"I managed to relax down the final part of the course and I have no problem with the silver."
After failing to finish in the super combined and super-G and managing 11th in the downhill, Fenninger was happy with her performance even though it left the host nation still without an individual gold medal.
"After the previous disappointing races, I didn't believe in my chances any more, so I decided I would just enjoy my skiing, have fun and not think about the results," she said.
"I had two solid runs, what helped the most was to hear the encouragement of the crowd."