The new line-up will replace the current cabinet that Kibaki assembled after Odinga accused him of rigging elections.
"My challenge to the new cabinet members and the entire national leadership at all levels is: let us put politics aside and get to work," Kibaki said, while announcing the replacement cabinet on Sunday.
"Let us build a new Kenya where justice is our shield and defender, and where peace, liberty and plenty will be found throughout our country."
Cabinet posts were divided between the PNU and ODM six weeks after a power-sharing agreement between the parties was brokered by Kofi Annan, a former UN secretary general.
Uhuru Kenyatta of the PNU and Musalia Mudavadi of ODM were named deputy prime ministers as well as ministers for trade and local government respectively.
Mohammed Adow, Al Jazeera's correspondent in Nairobi, said that the PNU appeared to have taken the "supreme ministries".
"The PNU ... has taken some key ministries including foreign affairs, the ministry of finance, the minister of interior security, defence and energy," he said.
"The ODM has taken the ministries of local government, immigration, roads and the ministry of public works, among others."
At least 1,200 people were killed and more than 300,000 were forced to leave their homes in violence that followed the disputed polls in December.
Kibaki pledged on Sunday that the cabinet would immediately task itself with helping people displaced by the post-election violence.
"We are ... facilitating the displaced people to resettle back on their farms as we support them and the surrounding communities with farm inputs such as seeds and fertilisers," he said.
|"One minister can have as many as three cars, huge offices, extravagant allowances in country where the majority of people live below one dollar a day"|
Wangari Maathai, Nobel Peace Prize winner
"The new cabinet will prioritise resettlement of the displaced people so that they can resume normal lives and play their part in nation-building," he said.
Civil society groups and newspapers have campaigned against the size of the cabinet.
Wangari Maathai, a Kenyan Nobel Peace Prize winner, said that the country could be managed more effectively by fewer ministers.
"The international community has no business giving money, giving advances to a government that uses that money not to develop, but rather to sustain an extravagant lifestyle," she said.
But Topi Lyambali, editor of the Kenyan London News, told Al Jazeera that a large cabinet was arguably necessary to promote stability.
"What many observers have been pointing out is that you cannot put a value to peace. Whatever it costs, the Kenyans have to get it," he said.
The public has grown increasingly impatient with Kibaki and Odinga.
For three days this week, fighting broke out in Kibera, Kenya's largest slum, between police and people protesting against the delay to form a coalition cabinet.
Naomi Wanjiku, who fled her home in the Rift Valley during the violence that erupted after the disputed election, asked why neither Kibaki nor Odinga had helped thousands of displaced people, before the announcement on the new cabinet.
She told Al Jazeera: "On the issue of the cabinet, I hear that they will be getting a lot of money. But they do not give us any, here we are living in tents. Don't they think?"