Kalla won the women's skiathlon in a time of 40 minutes and 44.9 seconds in an event combining 7.5 km classic and 7.5 km freestyle skiing.
Sweden's Charlotte Kalla claimed the first gold of the Pyeongchang Winter Olympics but the spotlight on Saturday was expected to fall on the unified Korean hockey team.
Bjoergen captured her 11th career Olympic medal, breaking a three-way tie with Raisa Smetanina of Russian Federation and Stefania Belmondo of Italy.
Kalla won the race by more than seven seconds, breaking away from the pack in the final 2 kilometers to avenge her loss to Bjoergen in the 2014 Sochi Olympics.
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Sochi Games champion Marit Bjoergen of Norway took the silver 7.8 seconds behind and Krista Parmakoski of Finland won the bronze.
And the victor of the PyeongChang Winter Olympics' first gold medal is.
The 26-year-old says, "I need to work on a few things to manage stress". She was too tough for me, so I think that silver was the best for me.
Meanwhile, Germany's Laura Dahlmeier, 24, won her first gold medal in biathlon, taking the women's 7.5km sprint, ahead of Norway's Marte Olsbu in second place and Veronika Vitkova from the Czech Republic in third.
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Kalla became the first Swedish woman to claim three gold medals at the Olympic Winter Games, which equaled Agneta Andersson as the Swedish woman with most Olympic gold medals. She will have a chance to pass that mark in the upcoming weeks.
The gold is Kalla's third and sixth Olympic medal of her career. The lead changed hands several times on the third lap before Bjoergen again grabbed the lead.
Wust could also become only the second Dutch athlete to successfully defend an Olympic title since the legendary Sven Kramer's back-to-back golds at 5000m in 2010 and 2014.
"There were some thoughts about what the others were doing but I just tried to focus on my performance", Kalla said.
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