A Labour government would introduce new "technical degrees", backed by employers and universities, aimed at young people who don't want to study traditional academic subjects, Ed Miliband said.
In a speech, the Labour leader said more needed to be done to help the "forgotten 50 per cent" who do not go on to university.
He outlined Labour's proposals for new practical degree courses, and announced that these qualifications will be the party's priority for the expansion of university places.
These "technical degrees" will be primarily aimed at young people who have already done apprenticeships and vocational qualifications and want to continue down this path, rather than a traditional academic route.
The courses will be co-designed by employers who will sponsor young people taking the qualifications.
Students taking the degrees, who may already have been working for the employer sponsoring them, will be able to earn wages while studying.
Speaking at a summit on vocational education in London, Mr Miliband said: "For too long governments have believed there is only one way to success through education which is to follow the conventional academic route: to do GCSEs, A-levels, a traditional academic subject at university and then on to career."
This route has worked for many, Mr Miliband argued, adding he is proud of Labour's record on expanding access to university.
"But that kind of aspiration cannot be limited only to those young people who choose a conventional academic route," he said.
" We must be one nation, not two, because we know that route doesn't work for everyone and we know as well there have not been clear enough alternatives.
"What do we say to a young person at school thinking about their career for the first time if they don't want to do traditional academic subjects? What is the gold-standard vocational qualification? What should they be aiming for in the long-run? What do they need to do to get there?
"We know other countries get this right. In Germany, there are proper, joined-up qualifications at every level - pathways on to apprenticeships and careers. Where other countries have succeeded, we have failed our young people."
Despite the fact that much of the vocational and technical expertise in the education system is in colleges and training providers, Mr Miliband did not mention any role for the FE sector in his proposals.
When questioned on this by TES, he said it was something he would "look at and consider."
"We will look at the question of how and where this is delivered, it's something we will consult on" he said.
Later, Liam Byrne, shadow minister for universities, told TES that FE colleges would be involved.
"There will be a pot of public money to help run these programmes, and will encourage universities and employers to bid for that," he said.
"We will encourage colleges to be part of that partnership. Employers like working with colleges because they are adaptive to changing needs. Over the summer we will develop these proposals further to show how well will bring a new level of integration between FE and HE, which is currently missing."
Mr Miliband told the summit that a Labour government, working with businesses and employers will "revolutionise learning and training" to build a high-quality, high-skill economy for the future.
In his address to the conference, skills minister Matt Hancock questioned Mr Miliband's understanding of the system.
"Can someone tell him [Mr Miliband] we are already building that technical education system?" he said.
"We already have technical degrees and over 200 FE colleges support HE learning.
"It's good to get bipartisan support for our skills reform but I think it's good to know what's happening in our skills system before talking about reform."