The government has announced plans to bring an additional 7.5 million people online by 2014 as part of its National Digital Participation Plan.
The initiative will target excluded groups, including those on low incomes, the unemployed, disabled and older people to narrow the "digital divide".
The Department for Business, Innovation and Skills (BIS) said 12.5 million people were missing out on the financial savings, education and employment opportunities and online public services that the internet made available.
Minister for Digital Britain, Stephen Timms, said: "Being online is crucial for participation in the 21st century society. The internet unlocks a wealth of information and services, giving people more choice in life and access to a range of education, health and financial opportunities."
BIS said a fully digitally skilled workforce was vital to business and commercial growth and improved the UK's ability to complete globally.
This week has seen e-Skills, the sector skills council for business and IT, call for a larger and better trained technology workforce. Jobs growth in IT is expected to be quadruple the national average.
The digital participation plan is supported by 60 public and private organisations including Ofcom, the BBC, Google, Sky, UK Online centres and Age UK.
Age UK's Digital Inclusion Network is providing one-to-one technology training to 200,000 elderly people through a collaboration with 170 voluntary groups.
Separately, the Department for Children, Schools and Families is spending £300m on free computers and internet connections to families with schoolchildren.