Maturana, who coached his native Colombia in the 1990 and 1994 World Cup finals, left because of "differences in opinion" with the Trinidad and Tobago Football Federation's executive committee, according to the TTFF.
Midfielder Russell Latapy will be the interim coach.
T&T, which qualified for the World Cup for the first time in 2006, has two points after three games in the Hexagonal and is tied with El Salvador for last place.
It blew a 2-0 lead and had to settle for a 2-2 tie with El Salvador in February. The Soca Warriors then needed a last-minute goal to earn a 1-1 tie at home with Honduras.
Maturana was appointed before the start of qualifying and finished with a record of 18 wins, 10 ties and just six losses in 34 games, but T&T also failed to qualify for the 2009 Gold Cup.
Former T&T national team coach Zoran Vranes has been appointed as Latapy's assistant.
The members of Maturana's technical staff, which included his brother Caesar and trainer Jorge Ruiz, also quit.