Salim Lone, spokesman for Odinga's Orange Democratic Movement (ODM), said the party leader had instead sent a four-person delegation to Kibaki for the talks on ending a month-long impasse over the cabinet line-up.
"Hon. Raila is not part of this delegation," Lone said.
The four ODM officials left Kibaki's city centre office minutes after they arrived. They said they had delivered a message from Odinga, but gave no other details.
The joint cabinet is central to an accord brokered in February to end the east African nation's post-election crisis, which triggered riots and ethnic attacks that killed at least 1,200 people and displaced 300,000 more.
Under growing local and international pressure for a breakthrough, Kibaki cancelled a trip to India on Monday to try to finalise a deal.
The new cabinet was initially due to be announced on Sunday, but Kibaki and prime minister-designate Odinga failed to agree on dividing up ministries. They had said they made "substantial progress" in talks, but many Kenyans were sceptical.
The shilling eased against the dollar to close at 62.35/45 to the dollar compared to Friday's 61.80/90 on fears there would be no deal on Monday.
The violence that followed Kibaki's contested victory at a December 27 election eroded Kenya's image as a stable, prosperous country and hurt its economy, currency and stock market.
On Thursday the rivals had agreed on how to share 40 ministerial jobs, but bickering broke out immediately.
Sources on both sides said most of the disagreement involved just a few ministerial posts. Each side will get 20.
One post not in dispute is finance, which means current Finance Minister Amos Kimunya is likely to keep his job.
In an editorial titled "Talks over cabinet becoming a charade", the leading Daily Nation newspaper warned that Kenyans' patience was running out.
"As long as the agreement is not actualised we cannot be confident that we are enjoying peace and normalcy," it said. "At the moment we are merely enjoying the respite of a ceasefire as our feuding leaders try to reach accommodation."
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