Simmons will return to Trinidad & Tobago to continue his rehabilitation, according to the West Indies Cricket Board (WICB).
The batsman was not picked in the playing XI for the first two ODIs and had only played a practice game against India A on the tour. The WICB is expected to announce a replacement for Simmons in the coming days.
Simmons, who last played a Test for West Indies in 2011, has not been a part of the five-day squad for the last couple of years but has featured regularly in the limited-overs matches.
The five-match ODI series between India and West Indies was reduced to four matches following the cancellation of the third ODI in Visakhapatnam due to a cyclone Hudhud. The teams are level at 1-1 after two games.