The Houthis and their allies from former president Ali Abdullah Saleh’s General People's Congress party announced the line-up of the 42-member body, which will be headed by former governor of Aden Abdel Aziz bin Habtoor.
The new cabinet was announced by the "supreme political council", which was established earlier this year by the rebels.
"[…] The government, which was formed amid the difficult conditions experienced by the country, is tasked with putting in order the internal situation and confronting the [Saudi] aggression," Houthi-run state news agency Saba reported.
"The Council noted that this comes amid the intransigence of the aggression and its [Yemeni] mercenaries to move within the framework of a national solution ... to spare the country further bloodshed and destruction."
The move is likely to provoke a strong response from the government of President Abedrabbo Mansour Hadi, whose forces have been battling the Iran-backed Houthi rebels and their allies since 2014.
It could also be a gesture of defiance aimed at the UN and US, which continue to advocate a national unity government that would include rebels and representatives of the Hadi camp.
The announcement came at a time that US-backed and UN-mediated peace efforts have faltered.
UN envoy Ismail Ould Cheikh Ahmed met the rebels in Muscat last week and was scheduled to meet Hadi in Aden, the southern port city and temporary seat of the internationally recognised government.
A previous round of peace talks held in Kuwait collapsed in August, and a 48-hour ceasefire declared by the coalition ended last Monday with little success in reducing the violence.
The UN says the war in Yemen has killed more than 10,000 people and wounded nearly 37,000 since March last year.