The series, also comprising three T20 Internationals, will mark Kohli's first assignment at the helm, since Mahendra Singh Dhoni relinquished the post earlier this month.
The series also holds importance from third-ranked India's perspective as it is the only opportunity for the limited overs specialists to make a mark before the International Cricket Council (ICC) Champions Trophy in England from June 1 to 18.
In between, India will play five Tests -- one against Bangladesh and four against Australia -- before the domestic T20 league (Indian Premier League) to be played from April 3 to May 26.
Going into Sunday's encounter, India will have the psychological advantage of thrashing the visitors 4-0 in the longest format while fifth-placed England will aim to win their first ODI series in the subcontinent since 1984-85.
On paper, both sides appear to be a formidable force with England winning the first tour match against a strong India A side led by Dhoni. India A returned the compliment under Ajinkya Rahane's captaincy when they hammered the visitors in the second game at the Brabourne Stadium in Mumbai.
In the absence of regular opener Rohit Sharma, Lokesh Rahul is most likely to partner Shikhar Dhawan at the top with Kohli, Yuvraj Singh, Rahane and Dhoni handling the middle-order.
After missing the limited overs series against New Zealand, all-rounders Ravichandran Ashwin and Ravindra Jadeja are set to return to the playing XI against England.
Seasoned pacer Umesh Yadav is likely to spearhead the pace bowling department along with Bhuvneshwar Kumar and Jasprit Bumrah.
On the other hand, after opting out of the Bangladesh tour, Eoin Morgan has returned to the helm for the visiting side which will have Jason Roy and Alex Hales opening the batting.
The middle order is likely to comprise Joe Root, Jonny Bairstow, Morgan, wicketkeeper-batsman Jos Buttler and Moeen Ali and an additional batsman in Sam Billings.
The bowling department will be headed by leg-spinner Adil Rashid, who is likely to have Chris Woakes, Liam Plunkett and a toss-up between the two all-rounders Ben Stokes and David Willey for company.
Moeen Ali can double up as a part-time off spin option if the pitch at the Maharashtra Cricket Association Stadium offers assistance.
After Pune, both sides will travel to Cuttack for the second ODI on January 19 and then to Kolkata for the final game on January 22.
The T20Is will be held in Kanpur on January 26, Nagpur on January 29 and Bengaluru on February 1.
India: Virat Kohli (Captain), Mahendra Singh Dhoni (wk), Shikhar Dhawan, Yuvraj Singh, Ajinkya Rahane, Lokesh Rahul, Ravichandran Ashwin, Ravindra Jadeja, Jasprit Bumrah, Kedar Jadhav, Bhuvneshwar Kumar, Amit Mishra, Manish Pandey, Hardik Pandya, Umesh Yadav.
England: Eoin Morgan (Captain), Alex Hales, Jason Roy, Jos Buttler (wk), Jake Ball, Chris Woakes, Ben Stokes, Joe Root, Moeen Ali, Sam Billings, Jonny Bairstow, Liam Dawson, Liam Plunkett, Adil Rashid, David Willey.