Under the new programme, job seekers who are still unemployed after two years will have their benefits reduced if they do not enrol on the Help to Work programme.
Steps they will need to take after this period include coming into the Jobcentre every day, taking community work and undergoing intensive employability training.
Work and pensions secretary Iain Duncan Smith said the move is about not "writing people off".
"Everyone with the ability to work should be given the support and opportunity to do so," he said. "We are now seeing record numbers of people in jobs and the largest fall in long-term unemployment since 1998."
He added: "But there's always more to do, which is why we are introducing this new scheme to provide additional support to the very small minority of claimants who have been unemployed for a number of years."
Employment minister Esther McVey denied the rules are about punishing people who fail to find work. But shadow employment minister Stephen Timms accused the Government of mis-diagnosing the problem, and called for help to be introduced earlier in the process.
"This Government allows jobseekers to spend up to three years claiming benefits before they get literacy and numeracy training," he said. "A Labour Government will introduce a basic skills test to assess all new claimants for jobseeker's allowance within six weeks of claiming benefits."
