Germany (Simon Lesser, Arnd Böhm, Daniel Peiffer and Erik Schempp) finished 3.5 seconds later to take silver, after a thrilling race for the line between Shipulin and Schempp.
Austria (Christoph Sumann,Daniel Mesotitsch, Simon Eder and Domenik Landertinger) came in a further 26.3 seconds back to take the bronze, denying defending champions Norway a place on the podium.
Going into the final leg, four teams were neck-and-neck. However, Norway's anchorman Emil Hegle Svendsen produced a poor final standing shoot, missing three out of five targets that effectively put his team out of contention for the podium.
Ole Einar Bjørndalen went into the relay knowing that victory for the Norwegians would give him a record-breaking ninth gold medal. And for much of the contest that looked like a distinct possibility.
Having completed a solid third leg, after missing no targets in both the prone and the standing positions, Bjørndalen handed over to Svendsen in pole.
But his team-mate then suffered a rare lapse on the shooting range which cost him a penalty circuit and pushed Norway out of the top three. At the finish he cut a distraught figure as he was consoled by his team-mates.
“I'm very sad. It was my fault,” said a distraught Svendsen. “I have no explanation.”
“It's very hard, of course, and I think it's most disappointing for Tarjei Bø and Johannes Thinges Bø who got us so high up,” he added, referring to the Norwegians’ first two legs, during which they had built a commanding lead.
Bjørndalen, meanwhile, was quick to come to his team-mate’s defence. “We'll try to support him,” said the 40-year-old.
“The fact that this happened to Emil who was so well prepared, shows it can happen to everyone, and it can happen to the best of us.”
For Russia, by contrast, there was unfettered joy, as their quartet delivered a first biathlon gold, for the hosts, who had gone into Sochi 2014 with especially high expectations.
Meanwhile, though Bjørndalen finished without another medal, he bowed out from Sochi 2014 having taken his overall Olympic tally to 13, setting a new outright record, and sharing the record of eight gold medals with his compatriot, cross country skier Bjørn Daehlie.