Rhiannon Wilkinson, head of Wycombe Abbey in Buckinghamshire, suggested it was best for girls' education to grow in a "boys-free" environment.
She added single boys hold girls back because girls mature faster.
"My wide educational experience in both mixed and girls' schools has shown me clearly that girls are best served educationally in their teenage years in a boys-free work environment," she was quoted as saying by the Telegraph.
"Most psychological studies suggest that girls and boys develop at different rates and that girls are far in advance of boys through the teenage years: it is in a girl's best interest to be educated separately, at least until boys catch up with her," she added.
Wilkinson said another benefit of an all-girls education is that they can focus on their education without the distraction of wanting to please boys.
She said, "In co-ed environments, lots of girls, when adolescence kicks in, want to be liked by boys not just for their intelligence and want to be popular with boys.
"In a girls' environment you're free from that. Most of the time you're focusing on your education, on who you are, you don't feel you're not being yourself in the classroom, you're not afraid to throw yourself in the sport field."
Her claims are backed up by a study quoted in The Guardian in 2009. This study found that the GCSE results of students of all-girls schools were significantly better than girls who studied in mixed-sex schools. The study also showed that students of all-girls schools were more likely to pursue technical subjects such as engineering and computer science in higher education.
The Guardian quoted one of the principals at the schools participating in the survey as saying, "It's a question of confidence in the way girls develop. It's cool to be very good at anything in a girls school - maths, sciences or physics. No one will ask why you're doing a boys' subject. Girls who lack confidence can thrive more in girls-only schools. We don't have boys competing and distracting, so girls can really go for it."
The study further recommended that girls-only schooling could greatly benefit girls who are struggling academically.
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