ST Pius is one of five local schools to be included in the first phase of the Building Schools for the Future programme.
It will be rebuilt or undergo a major refurbishment scheme within three years, as will four other schools in Rotherham.
Building work was due to start in 2013 but has been brought forward two years because the council were given the opportunity to bid earlier than planned.
The council and the schools, along with other partners, will produce plans for the works so they can confirm how much Rotherham will receive from the Department for Children, Schools and Families to fund the BSF programme.
Coun Shaun Wright, a Cabinet member, said: "This is absolutely fantastic news for the borough and shows the positive view of Rotherham on the national stage when it comes to regenerating our schools. "We have seen the way new buildings have transformed lives for hundreds of staff and pupils at schools around the borough and this multi-million pound injection of funding will mean we can continue." John Healey, MP for Wentworth, added: "We are already seeing the big impact that investment can have in our Rotherham schools. This will be another massive boost to bring about the facilities that our students need for the future. "Our young people and teachers deserve the best possible facilities and buildings to learn and teach in and the best equipment. This is the Government making good its promise to make education its highest priority."