“I want to thank you, my fellow Kenyans, for your tolerance and patience during this period,” Mr Kibaki said in a televised speech.
“I’ll do everything possible to ensure our country Kenya is steered along the path of peace, unity and stability.”
He retained Finance Minister Amos Kimunya in the 40-member government line-up, and confirmed Mr Odinga, of the Orange Democratic Movement, as prime minister.
The naming of a power-sharing cabinet is central to a deal ending the east African nation’s post-election crisis. More than 1,200 people died and 300,000 were uprooted in what became the country’s bloodiest episode since independence in 1963.
Uhuru Kenyatta from Mr Kibaki’s coalition and Musalia Mudavadi of Mr Odinga’s party were named deputy prime ministers. William Ruto, another opposition figure unpopular with many Kibaki aides, was appointed agriculture minister.
“My challenge to the new cabinet members, and to the entire national leadership at all levels, is let us put politics aside and get to work,” Mr Kibaki said.
“Let us build a new Kenya where justice is our shield and defender and where peace and liberty and plenty will be found throughout the country.”
Violence exploded after Mr Odinga accused Mr Kibaki of rigging the December 27 presidential election.
The electoral fight degenerated into ethnic killings and riots that shattered Kenya’s image as a stable tourism and trade hub, with one of sub-Saharan Africa’s most promising economies.
Mr Kibaki, 76, and Mr Odinga, 63, met in secret on Saturday at Sagana State Lodge, a fishing retreat 100km north-east of Nairobi to end a six-week impasse.
The two leaders had agreed to appoint a cabinet on April 6, but the deal fell apart at the last minute, unsettling Kenyans and investors fearful of a return to violence.
The two men have come under local and international pressure to break the deadlock on the cabinet, part of a deal brokered in February by former UN Secretary-General Kofi Annan.
During the week since the first cabinet agreement fell through, Mr Kibaki and Mr Odinga called for calm and argued their positions were not far apart.