A "hit squad" of specialist advisers will be based in jobcentres to deal with people not in a sustained job after spending two years on the Work Programme.
Under the plans, claimants will lose their benefit if they refuse to go on a training scheme or mandatory work activity placement within days of finishing the Work Programme.
Ministers said £30 million will be available to pay for extra training and specialist help on areas such as counselling for people dependent on drug and alcohol.
Employment Minister Mark Hoban said: "The Work Programme is getting some of the hardest to help claimants into work despite a tough economic climate. We always knew that there would be some who would require further support after the Work Programme, which is why we're introducing this intensive and uncompromising regime.
"We'll be stepping up the pressure on claimants, who will be expected to attend the jobcentre more frequently, with rigorous monitoring to ensure they are doing everything they can to find work."
The Work Programme, launched two years ago, has come under fire over its performance. MPs on the Work and Pensions Committee said in a report earlier this month that the scheme appeared to be failing the most disadvantaged jobseekers.
Their report said support for the mainstream jobless was getting better after a poor start, but it said there was growing evidence service providers were "parking" the most disadvantaged people.
New figures showing how the programme is performing are due to be published at the end of June.