Muirhead, alongside Anna Sloan, Vicki Adams and Claire Hamilton, narrowly defeated Russian skip Anna Sidorova 6-5 in their last round robin game to leapfrog them into second overall.
Leading 2-0 after the first end, Muirhead found herself 4-2 down by the third as Russia scored three then one in the next two ends before the Scot responded with two of her own in the fourth.
They added another in the sixth to take a 5-4 lead and, with Russia pulling level in the eighth, Muirhead’s rink scored the decisive winning point in the tenth and final end in Karlstad.
That represented Muirhead's fourth successive win at the championships and, third going into the final round of fixtures, helped her rink finish second overall behind hosts Sweden.
Muirhead will have the momentum going into the page one-two play-off with Swedish skip Margaretha Sigfridsson as her rink lost their final round robin game 7-5 to Linda Klimova's Czech Republic.
And Muirhead, who led the exact same Scottish rink of Sloan, Adams and Hamilton to the European title in Moscow last year, agrees that they are hitting form at the just the right time in Sweden.
"We came out sharp. We got the hammer and we took our two in the first end. Their three came out of nowhere, she played two perfect shots and got three on the measure," said Muirhead.
"But we did not let that faze us, it was not the end of the game so we got our two back and forced when we had to force, and got the ideal situation at the end.
"We controlled that. I think even just our body language showed that we wanted it more. All in all, it was a solid performance by all of us.
"Our goal was to get into the one-two game, which we've done. The girls are playing great and leaving me simple shots, which I like."
Meanwhile Russian skip Sidorova will face the winner of a tie-breaker between Denmark's Lene Nielsen and Switzerland's Mirjam Ott in the page three-four play-off.
Ranked joint-fourth ahead of the final fixtures, Ott's 10-5 victory over German Andrea Schoepp and Nielsen's 9-1 win over Finland's Anne Malmi forced a decider between the two in Karlstad.
And in the final round robin fixture Italian Diana Gaspari claimed her fourth win of the championships with a 10-5 victory over Ildiko Szekeres of Hungary.
In the men's competition, Tom Brewster guaranteed Scotland a place at next year's World Curling Championships with victory in their last game at the Europeans, but there was no hiding his overall disappointment.
Out of contention for the page play-offs before their final fixture against Hungary having lost five and won only three, skip Brewster ensured Scotland beat Hungary 6-5 in Karlstad.
Brewster put Scotland into a 3-1 lead when he hit for two points in the fourth end and, despite single steals for Hungary in both the ninth and tenth, the contest was to finish 6-5.
With the top eight at the Europeans qualifying for the worlds in Canada in the spring, the win ensured Scotland seventh but Brewster admitted he expected far more in Sweden than that.
"Qualification? That's great, but ultimately we did not come here just to do that, we came here to win medals and we're disappointed we're not in the play-offs," said Brewster.
Meanwhile as the round robin of the men's competition came to a close Sweden's Niklas Edin defeated defending champions Norway and Thomas Ulsrud 7-6 in a tight contest to top the rankings.
Edin's rink will now face Jiri Snitil in the page one-two play-off, the Czech Republic skip seeing off Denmark's Rasmus Stjerne 7-6 to guarantee second in the table in Karlstad.
Stjerne will play Norway's Ulsrud in the page three-four play-off while elsewhere in what was a relegation decider to Division B between France and Germany, the former succeeded 12-9.
And in the remaining fixture Switzerland, who were still in the medal hunt when they entered the ice in Sweden, lost 8-6 to Russia and skip Andrey Drozdov.