Bihar Chief Minister Nitish Kumar submitted his resignation to Governor Rajendra V Arlekar on Sunday morning, officials said.
The governor accepted Kumar's resignation, and asked him to continue as caretaker CM till a new government is formed, they said.
Kumar was accompanied by senior minister Bijendra Yadav of the JD(U) when he went to the Raj Bhavan.
Kumar submitted his resignation after chairing a meeting with party MLAs at his official residence.
A new government with the support of the BJP is likely to be in place by the evening, according to sources.
"Will leave the earlier alliance and form a new alliance," said Nitish Kumar after resigning as Bihar CM.
"Kumar is likely to resign after chairing a meeting of JD(U) MLAs at his official residence on Sunday," party sources said earlier.
Kumar was expected to address the meeting after 10.30 am, they said.
"Offices, including the Governor's secretariat, have been ordered to remain open on Sunday in view of the likelihood of hectic activities", said the source who claimed that Kumar, who has maintained a deafening silence over the political turmoil in the state, had "confided in trusted aides about his next move "a couple of days ago".
As Kumar's return to the BJP-led NDA, which he had vowed to defeat, looked imminent, a rattled RJD held a meeting of its leaders to take stock of the situation and chalk out a future course of action.
Meanwhile, Janata Dal (United)'s political adviser and spokesperson K C Tyagi told reporters in Delhi that the grand alliance government in Bihar is on the verge of collapse, and accused a section of the Congress leadership of repeatedly "insulting" Kumar.
"The INDIA bloc is on the verge of collapse. The alliance of INDIA bloc parties is almost over in Punjab, West Bengal and Bihar," he said.