Obama called that "an illusion" because, he said, such workers are often better qualified and better educated than workers who just recently lost their jobs.
Obama also signed a presidential memo directing the federal government not to discriminate against those long-term unemployed workers in its own hiring practices.
The event and the memo illustrate the types of targeted, non-legislative measures Obama promised to undertake to expand economic opportunity during his State of the Union address earlier this week. Obama has declared 2014 a year of action for his administration, but his chances of winning legislative victories are slim in in an election year and with a divided Congress.
He renewed his call for Congress to reinstate jobless benefits for the long-term unemployed, noting that it is a way to keep workers financially afloat while they pursue jobs. The benefits ran out at the end of December. Lawmakers have been debating how to pay for the cost of the benefit and for how long to make it apply.
Among the CEOs at the White House Friday were top executives from eBay, Morgan Stanley, Boeing, Marriott International and McDonalds.
Although the overall national unemployment rate has declined to 6.7 percent, long-term joblessness in the U.S. remains a major problem. The concern is that the longer someone is out of a job, the harder it gets to find a new one. Companies are less likely to hire people who haven't used their skills in months or wonder why another employer hasn't already snatched them up.
"Just because you've been out — been out of work for a while does not mean that you are not a hard worker," Obama said. "Just means you had bad luck or you were in the wrong industry or you lived in a region of the country that's catching up a little slower than others in the recovery."
With that concern in mind, the Obama administration has been working for months to exact commitments from companies to ensure their hiring practices don't discriminate against long-term job-seekers.
That includes doing away with candidate-screening methods that disqualify applicants based on their current employment status. It also means ensuring that job ads don't discourage unemployed workers from applying.
The White House couldn't say how many unemployed Americans might benefit from the initiative but expected the effects to snowball.
"We consider this not the destination, but the launch," said Gene Sperling, who heads the White House's National Economic Council. "Our hope is that as people see the meeting with the president, the pledge, that more will come work with us."
Among the companies taking part: Rupert Murdoch's News Corp. and 21st Century Fox. Sperling said he emailed the conservative business mogul about the initiative, and Murdoch personally wrote back to say he supported it.
The Obama administration will direct $150 million in grants toward partnership programs that retrain, mentor and place unemployed workers.