The Scot, who won European, World and Olympic honours during a glittering career, has described the move as "the hardest decision" of her life.
The 32-year-old took to social media to make the announcement, saying: "After 15 years of International Curling and 21 International titles, I have made the hardest decision of my life to hang up my curling shoes and retire.
"Throughout my career and like most athletes, I have experienced both the highest of the highs and the lowest of the lows and at times the future seemed very distant. It's been an emotional journey but a journey that I am incredibly proud of."
Muirhead was part of the Great Britain team which claimed gold at the 2022 Winter Olympics in Beijing.
As captain, she claimed the elusive gold after four unsuccessful efforts. Victory at the Games was undoubtedly the pinnacle of a career which saw Muirhead become the most decorated curler in Scotland's history.
Scotland's Olympic hero also won three European championship titles and became the world mixed doubles champion earlier this year alongside playing partner Bobby Lammie.
In her retirement statement, Muirhead added: "Behind every athlete is a team and I have had the opportunity to work with some of the best and therefore there are many thanks to be made. I can't thank everyone here, but will do so individually I hope over the coming weeks.
"To every single teammate I have had the privilege of playing with, I would like to thank you for your hard work and dedication, this comes from the bottom of my heart."
She added: "Retiring from curling as current European, World and Olympic champion is something I always dreamt off, and I am signing off with a huge smile on my face.
"With regards to what's next… I'm looking forward to exploring more opportunities and getting my golf clubs out… but watch this space!"