Defending champion Martina Sablikova of the Czech Republic took silver, while Russian Olga Graf won an emphatic bronze.
Graf had briefly threatened to cause an upset and send the home crowd into raptures as she blitzed around the Adler Arena. The 30-year-old clocked a time of four minutes, 3.47 seconds.
Women's 5,000-Meter Speedskating Results
1. Ireen Wurst Netherlands 4:00.34
2. Martina Sablikova Czech Republic 4:01.95
3. Olga Graf Russia 4:03.47
4. Claudia Pechstein Germany 4:05.26
5. Annouk van der Weijden Netherlands 4:06.73
6. Ida Njaatun Norway 4:06.77
7. Antoinette de Jong Netherlands 4:09.36
8. Yuliya Skokova Russia 4:09.39
9. Shiho Ishizawa Japan 4:10.02
10 Jilleanne Rookard USA 4:10.17
Sochi2014.com
Despite the eight skaters to come, the home athlete's time was just enough to cling on for a bronze medal and secure the host's first medal of the Games.
Sablikova topped Graf's time as she came home in 4:01.95, but she did not hold on to pole position for long as Wust stepped onto the ice next.
The Dutch skater, who won over the same distance in 2006, blew away her Czech rival by over 1.5 seconds in 4:00.34. Among the spectators at the Adler Arena, Wust was cheered home by King Willem-Alexander of Holland.
So impressive was Wust's display that Sablikova clapped her rival off the ice, as reported by the Associated Press' Paul Newberry, via ABC News. Sonali Karnick of CBC Radio One in Quebec tweeted her appreciation of Wust's victory.
The victory reaffirms the Netherlands' superiority on the ice, as they completed a 1-2-3 in the men's 5,000 meters Saturday. The win also sent the Netherlands up to second in the medal table, with four, two of which being gold. All of those medals have come at the Adler Arena.
Elsewhere, 41-year-old Claudia Pechstein missed out on winning a remarkable 10th Olympic medal. The German struggled to stay in contention over the final laps and eventually had to settle for fourth with a time of 4:05.26.
But for Wust, it was a third taste of Olympic glory, with another shot to come in the 5,000-meter event on Feb. 19. Fans should expect her to be ready, just as she announced on Twitter and Instagram Saturday heading into Sunday's event.
She will also go for the 1,500-meter event, where she is hot favorite to take home gold. And it is difficult to see past Wust leading home the Dutch pursuit team to gold.
If Wust can add one more gold to her resume, she would join Fanny Blankers-Koen one of the most successful Dutch Olympic athletes of all time on four gold medals.
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