Evidence suggests those who believe they want to go to university at a young age are much more likely to do so.
Targeting girls before they move to secondary school can prevent them drifting away from “STEM” subjects – science, technology, engineering and maths – in later years, supporters say.
A senior Government source said: “Children who already know at 10 that they want to go to university are six times more likely to get there. It is about aiming high while young.”
The push comes ahead of a revolution in careers education in schools which will see business leaders drafted in to guide students.
Ministers want to put an end to careers advice being doled out as an “afterthought” by PE teachers.
One-on-one mentoring with leading professionals will be offered to pupils across the country.
“There is a real benefit to meeting people from diverse workplaces,” an insider explained.
Ministers also want young people to be able to harness technology to learn more about different careers.
Under the proposals they would be encouraged to talk via Skype to a range of professionals about what their job entails, from nurses to mechanical engineers to artists.
Large employers will also be asked to offer work experience placements to pupils, as well as providing multiple mentors.
The changes are expected to be announced in a new careers guidance strategy to be published later this year.
A source said: “This is an incredibly important area and one that we know is crucial to get right.
“We know if children come into contact with four people who do different jobs, that really changes their ability to make decisions about their futures.”
The DfE is working on the scheme with business groups like the CBI. Education Secretary Justine Greening said the careers strategy will have a “clear focus on driving social mobility”.
Earlier this year the Teach First charity called for careers education to be reformed, with more guidance and work experience offered to students from the most disadvantaged backgrounds.
Research commissioned by the group, carried out by pollster ComRes, discovered just 32 per cent of the most disadvantaged students thought their careers advisers had been helpful.