The swearing-in is scheduled at 10 AM at Raj Bhavan.
The expansion comes after a meeting Maharashtra Chief Minister Prithviraj Chavan held with Congress president Sonia Gandhi in Delhi, in the wake of the drubbing the ruling alliance suffered in the Lok Sabha polls.
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Chavan was sent from Delhi to take over reigns of the state in 2010.
The poll results saw Congress getting its lowest tally of just two of the 48 Lok Sabha seats in the state.
With the sacking of state Medical Education Minister Vijaykumar Gavit, one Cabinet rank of NCP is vacant.
Besides, the term of Minister of State for Education, Health and Culture Fouzia Khan as MLC has ended. There had been complaints against her for non-cooperation with official NCP candidate in Parbhani during the recent Lok Sabha polls.
The sources said senior NCP leader Suryakanta Patil is in race to fill in the Cabinet post while state NCP working president Jitendra Awhad and Sharad Gavit, Samajwadi Party MLA and brother of Vijaykumar Gavit, are in race to replace Fouzia Khan.
Meanwhile, legislators Amit Deshmukh, son of former Chief Minister late Vilasrao Deshmukh, Kalyan Kale and senior leader Rohidas Patil are among the probables from the Congress, which has three ministerial berths vacant, including one Cabinet.
The Assembly elections in Maharashtra are due later this year.