The 40-year-old Norwegian, who had equalled compatriot Bjoern Daehlie's all-time record of 12 Winter Games medals by taking gold in Saturday's 10km sprint, finished behind winner Martin Fourcade of France, with Ondrej Moravec of the Czech Republic taking silver and another Frenchman, Jean Beatrix, pipping him for third in Rosa Khutor on Monday night.
It was the first Winter Olympic gold medal for Fourcade, a five-time world champion, who had finished in a disappointing sixth place in the opening sprint race.
Bjoerndalen will have as many as four more chances to beat Daehlie's record, continuing with the men's 20km individual on Thursday.
Maria Hoefl-Riesch won her second successive Winter Olympics gold medal in the super combined after producing a stellar run in the slalom at Rosa Khutor Alpine Center.
The German, who carried the flag for her country at the opening ceremony, found herself in fifth after the downhill, with a time of one minute 43.72 seconds putting her 1.04secs behind discipline winner Julia Mancuso.
But Hoefl-Riesch underlined why she is thought of by many as the finest skiing all-rounder, with a blistering run in the slalom that sealed top spot.
An overall time of 2:34.62 ensured she edged out Austria's Nicole Hosp by 0.4secs, with American Mancuso, who finished a further 0.13secs back, settling for bronze.
It is Hoefl-Riesch's third Olympic gold as she also added the slalom crown to her super combined title at Vancouver 2010.
Hoefl-Riesch was understandably delighted with the result, especially after a disappointing downhill.
''This feels like a fairy tale. I am so happy about winning gold,'' she said.
''I can't quite believe it. This is really overwhelming. My confidence was a bit knocked before I went down, especially because the downhill didn't go great.''
The second gold medal decided on Monday afternoon was in the men's 1500 metre short track, with Canada's Charles Hamelin skating off with the spoils to add to the two gold medals he won in Vancouver four years ago.
Hamelin had qualified as the quickest racer from the three semi-finals earlier in the day, and the 29-year-old lived up to his favourite tag by clocking 2:14.985 in the showpiece.
Han Tianyu claimed the silver medal with a time of 2:15.055, with home favourite Victor An completing the podium.
Hamelin said afterwards: "It's not my best distance, but I had a really good start and was able to control the race afterwards."
Michel Mulder claimed Holland's first Winter Olympic gold in the 500m speed skating in the event's 90-year history.
The 27-year-old held off countryman Jan Smeekens and twin brother Ronald as the Dutch claimed a clean sweep of medals.
Canada claimed a one-two in the final of the men's moguls, but Russia's Alexandr Smyshlyaev denied them a clean sweep of medals in the freestyle event.
Smyshlyaev threw down the gauntlet to the Canadian trio in the final on the third and last run, mastering the softening course to score 26.31 and a mark of 81.13 percent.
Defending champion Alex Bilodeau topped that, however, with a points total of 26.31 giving him an overall mark of 87.70 percent, with last-man down Mikael Kingsbury then snatching silver with 82.36 percent.
Kingsbury's run pushed team-mate Marc-Antoine Gagnon out of the top three, with his final mark of 77.83 percent falling short of Smyshlyaev.
In the Ice Cube Center, the curling competition got under way for both the men and women. In the men's event, world champions Sweden gained the early advantage with wins over Switzerland and Great Britain, while their female compatriots, defending their Olympic title, got the better of Eve Muirhead's British rink 6-4.
Monday also marked the start of the women's singles luge at the Sanki Sliding Center. As expected Germany dominated the first two runs of the competition, with Natalie Geisenberger (1:39.814) topping the standings ahead of compatriot Tatjana Huefner (1:40.580).
Erin Hamlin of the United States was third, 0.818secs behind the leader, with the final two runs to decide the medals taking place on Tuesday.
Qualifying for the women's ice hockey continued to gather pace as powerhouses Canada beat Finland 3-0 and the United States routed Switzerland 9-0.