Rosi Sexton was the first British female to fight in the UFC in 2013, and McCann made her debut five years later.
McCann, who is a former flyweight champion in UK-based promotion Cage Warriors, won seven of her 14 bouts in the UFC, with her highlights including two spinning elbow knockouts in 2022.
She leaves the sport having won six of her bouts by knockout and claiming three performance-of-the-night bonuses, the most in UFC flyweight history.
McCann said she wanted to retire at home with her friends and family in attendance.
“The camps are too hard and, to keep it all together, it’s too hard to not get the wins and take the damage,” she said.
Her retirement comes after four defeats in her past five fights.
“UFC and Dana (UFC president Dana White), I started this sport at 24 and I have given you all my heart and soul,” said McCann.
“Tonight, with that performance on a week’s notice, it’s not good enough. The UFC deserves more.
“From a little girl from Norris Green fighting in arenas – look at me, look at what I’ve managed to do.”