The move follows concerns that girls as young as four are being forced to wear the Muslim headscarf to school.
Ofsted chief Amanda Spielman fears that schools may be in breach of equality laws if young girls were required to wear religious garments while boys were not, The Sunday Times reported.
"In seeking to address these concerns, inspectors will talk to girls who wear such garments to ascertain why they do so in the school," Spielman said.
Spielman has also called on parents and the public to complain to head-teachers if they think schools are not treating girls and boys equally. If the school does not take the complaint seriously, the complainants should go directly to Ofsted, she says.
A Sunday Times survey revealed that nearly a fifth (18 per cent) of 800 state primary schools in 11 regions of England list the hijab as part of their uniform policy, mostly as an optional item.
One of the country's top state primary schools, St. Stephen's School in east London, revealed it had banned the hijab for girls under eight last year, despite protests by parents and intends to ban it for girls under 11 from September 2018.
"There is no requirement for girls to wear the hijab until puberty. It is not appropriate in a primary school," said Neena Lall, head-teacher of the school where most pupils are from Indian, Pakistani or Bangladeshi backgrounds.
The Ofsted chief announced plans to evaluate the hijab policy in schools after meeting British Muslim women and secular campaigners who are calling for a ban on the wearing of hijabs in primary schools. Some fear the rise of the classroom hijab is a sign of Islamic conservatism asserting itself in the UK.
"Covering of young girls is often the first sign of young people being treated unequally. This often leads to girls being pulled out of swimming lessons, dance classes or other creative lessons," said Amina Lone, a former Labour party parliamentary candidate who was among those at the recent Oftsed meeting.
The UK's Department for Education said that it was up to schools to set their own uniform policies.
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