After the mixed double's narrowly missed out to Sweden in the bronze medal playoff match earlier this week, attention turned to the women's team to pick up a medal in the curling.
However, they got off to a bad start on Thursday morning after narrowly losing out to Switzerland in the opening round.
Muirhead, Vicky Wright, Jen Dodds, and Hailey Duff had been in control at 4-2, but struggled to seal the victory as mistakes started to creep in.
A number of miscued attempts allowed Switzerland to claw themselves back into contention, and then Swiss skip Alina Paetz landed a single to take the game to an extra end.
A cagey extra end left Muirhead with a pressure shot for the victory, but while she managed to get the line right, too much weight saw it glide agonisingly past the Swiss scoring stone.
It left Team GB with a loss in the opening round of the event, which sees nine teams go head-to-head in a round robin format, with the top four then progressing to the semi-finals.
However, while the loss obviously dents their chances of reaching the final four, Muirhead refused to be too downhearted about the defeat.
"They are never easy to judge," Muirhead said of the crucial shot. "Unfortunately it didn't come off. If I ever had a shot like that again, I'm confident I would make it."
"There's a lot of hunger here," added Muirhead. "A fourth Olympic Games is something that you dream of coming to.
"I'm very glad that I've got the opportunity to be here with four girls at their first Olympic Games.
"I'm proud of them, how much they've come along and fought and they deserve their spot in the team."
The women's team are back in action on Thursday, with their second group match against Sweden taking place at 12:05 GMT.