It has replaced incumbent EDComms with Weber Shandwick to spearhead the strategy, following a competitive pitch.
The DfES's business development unit will now focus on the UK's largest 300 firms in the UK to promote sponsorship and partnership deals, involving programmes such as skills councils and city academies.
Also included in the new brief is an attempt to encourage firms to get involved in childcare initiatives and school issues such as tackling truancy.
DfES head of stakeholder management Stuart Dickenson, who heads the unit, said: 'The previous direction didn't have this concentrated focus on the larger companies and was more about school partnerships.
'The reason is very much to build long-term partnerships and this has much more emphasis on vocational training and brings in other strands such as childcare.'
WS account director David Mencer said a key strategy was to promote the corporate social responsibility aspect to companies as well as the benefits in terms of recruitment.
He said: 'It helps business if the workforce is better skilled and business has a vital role in making that happen.'
With the general election pending, the DfES is holding off announcing details of which firms will be targeted in particular.