The 31-year-old right-hander, who is a top order batsman, has a back problem and a replacement player will be named in the coming days.
The withdrawal of Simmons follows those of experienced batsman Darren Bravo, off-spinner Sunil Narine and all-rounder Kieron Pollard.
West Indies play English county Warwickshire in Dubai on Sunday before travelling to Kolkata on Monday ahead of the World Twenty20 in India, which begins on Tuesday, March 8 and runs until April 3.
They are in Group 1 along with England, Sri Lanka, South Africa and a qualifier.
Revised West Indies squad
Darren Sammy (captain), Samuel Badree, Sulieman Benn, Carlos Brathwaite, Dwayne Bravo, Johnson Charles, Andre Fletcher, Chris Gayle, Jason Holder, Ashley Nurse, Denesh Ramdin, Andre Russell, Marlon Samuels, Jerome Taylor